AGC Book 20% Cyan Karl Fischer Titration

GTP Brochure

Good Titration Practice™ in Karl Fischer Titration

EDITORIAL

Dear Reader METTLER TOLEDO has an excellent knowledge in any kind of moisture and water content determination from % to ppm. It is of crucial importance to select the right analytical method in order to obtain reliable results that ensure quality and properties of the products in a multitude of industries. Karl Fischer titration is the method of choice for water content determination. With the new generation of METTLER TOLEDO compact volumetric and coulometric Karl Fischer Titrators V20/V30, C20/C30 and Excellence combined general and volumetric KF titrators T70 and T90, water determination has reached an unrivaled level of simplicity and security. This helps you to perform your daily tasks in the most optimal way. In this brochure a specific focus is put on how to perform the Karl Fischer titration analysis the correct way. We would like to introduce this to you as part of ‘Good Titration PracticeTM (GTP) in Karl Fischer titration. This brochure comprises detailed background information and recommendations about: • • • • • Chemistry and control of the Karl Fischer titration Practical tips and hints on sample preparation and instrument operation Measures to optimize accuracy and precision of the water determination Selection of the optimal method for water determination of your specific sample Trouble shooting recommendations if results do not coincide with the expectations

This GTP brochure in combination with the application brochure 39 should serve you as powerful tools for trouble-free water determination throughout the whole lifetime of your METTLER TOLEDO KF titrator. We wish you great success and enjoyment

Hans-Joachim Muhr Market Support Manager BA Titration

Rolf Rohner Marketing Manager BA Titration

.........................................12 3 Titration control and end point determination.........................2.............................................................................1.........2 Working with the coulometric KF instruments ...........................5 The solvent................................3 Pyridine-containing reagents .............4 Control parameters in the volumetric KF titration ...........5 1.........................2.........................................33 4.....................................................11 2.........4..............................................................4.....16 3.....................................................METTLER TOLEDO Good Titration PracticeTM in KF Titration Contents 1 Fundamentals of the Karl Fischer titration ...............................................1 An historic overview .........................................................................1 KF coulometry ......................19 3......................11 2.......................2.34 4........................................................28 4...............................................5 Limitations for the use of the cell without diaphragm................2.2.1 Volumetric KF reagents.........................2 The minimum and maximum dosing rate ......................................................................................2 End point and polarization current......7 2...................28 4.........................................10 2...............................6 General recommendations ...............2...............16 3..........................2 The drift ..0 mg/g ................................................................................................................36 4...1 The Control Band ......................27 4............1 The influence of atmospheric humidity (drift determination) .....................................19 3........................................1 Principle of bipotentiometric indication ......3.1 Titration stand .............................2 Reaction rate .........................................................19 3........................3 The Cautious start .....................................3................................................................4.......................................................37 4............................2 When do you have to replace the electrolyte? ..........2................3 Volumetric KF Titration: Titrant concentration............2...................................................................................................................................33 4.............3 Consequences for practical applications........................4...................2 Two-component KF reagent ..........3................38 5 Sampling ......9 2...................6......1........9 2..................1....................................................................35 4.............39 1 .............................4 Cleaning the coulometric KF titration cell........22 3............................................2 The Karl Fischer chemical reaction ..........................................20 3......................4 Special reagents for aldehydes and ketones........................32 4.........3 Secure draining and filling of the titration cell: SOLVENT MANAGER........8 2...................1 One-component KF reagent ..................................3............................4.............5 Karl Fischer reagents with ethanol ...........................3 Concentration determination with Water Standard 10...............3 Iodine generation...............1...4 1......9 2.........5 Application tips ......................................4 1..............14 3...........13 3.......1..8 2...................1.......................18 3...................................................................................13 3...........................1 Filling the coulometric cell ...............................................................2 Stoichiometry of the coulometric KF rection ......3......8 2.......6 2 Volumetric and Coulometric Karl Fischer Analyses ................................................29 4.........................1 How often should the concentration be determined?.....................24 4...........26 4..5 Control paramaters in the coulometric KF Analysis ...2 Coulometric KF analysis.............................................21 3....................................1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration .........6 Termination parameters for both coulometric and volumetric KF titration........2 Concentration determination with di-sodium tartrate dihydrate................................................................................1......7 2........................................................... The Karl Fischer titration.....................................................26 4..........4.............................4 Generator electrode without diaphragm ..................................................................3..........................................3 Stirring speed and dispersion of the volumetric KF titrant...........................................1.................21 3.......................2............................................7 2.............................................................18 3...................................29 4..................13 3.....26 4......5 Cleaning the measuring electrode ............................................................................................4 Concentration determination with pure water...................1........4 Polarization current and end point............1 Indication ............................................................................2........................................................6 Dissolving capacity of the solvent .........................33 4.

.............................................................................................3 Liquids: Characteristics ..........................................................................1................................................................................77 11..............1 Liquid samples ........................................3 Amount of sample .............71 9...........................................................................................4 Manual Karl Fischer drying oven...................................................................................................................................................................................................2 Liquid samples .............................79 11...5 Additional literature ...................................................................................................................83 11..................................................62 8 Measurement results ...........59 7..2 Side reactions .............................................................................81 11.............................................................3........................................................................75 11 Karl Fischer Titration: The Method at a Glance ..........................................................................58 7..........................................................................71 9..................................................................4...................1 Coulometry.....2....................1 Principle ..............87 11.......................................................................................................................................4....................................................................1.............79 11.........................6 References.............4 Example: reevaluation of side reactions .............................................................6...68 9 Interferences .....................................................1 Organic Chemicals...............................................................................................................2 Purge gas.....................................86 11.........................................................................................1 Solids: Characteristics.............................METTLER TOLEDO Good Titration PracticeTM in KF Titration 5....................inorganic .........57 7.............................................1 Internal extraction .............................................................................................................49 7..........................................................................................................................................4............................70 9..............1.............................................................................................................................................................................................70 9...................................................................................................55 7..........87 11...................2 Storing the sample ...............................79 11.4 Technical products .................................47 7..........................................................................................................2 Reaction with water.....................................78 11....90 2 ........1 Organic and inorganic chemicals ....................................73 10.......................72 10 Troubleshooting ...4.............................2 Solid samples................39 5................................89 12 Appendix ........................2 External extraction ...........................58 7.....................................................................3 Titration Methods ..83 11.............................................................4 Lyophilized substance in septum bottles...............................................................4 Sample preparation and input ............2 Measurement accuracy................................................................................6.................77 11..................67 8.............................88 11.........................54 7....................................80 11.........................................................................1 Solid samples..........................................................1 Taking the sample...............1 Resolution and detection limit ............................43 6......40 6 Sample addition ...................................................43 6......73 10.....71 9..................................................3 Procedure....................70 9.....4...................................................3 Repeatability .......................5 Determination of water in gases ....................2............................86 11......60 7..87 11..........................................................................................67 8............................4...................................................6......1 Volumetric methods ....................................................................................................................................................85 11......................................................................................................................................................................................2 Inorganic chemicals ..........5 Accessories for sample input ......................................................................................................................................................................................................2 Coulometric methods .............1...............................5 STROMBOLI automatic oven sample changer ...........2 Volumetric Karl Fischer Titration ................67 8................................2 Solids: Sample input .2 Foods and technical products ..................6..........................................................................................................................................80 11.................4 Liquids: Sample input.............1...........39 5...........................................6 Food ....3..................6........................................3 External dissolution ..2.....1 Effects of temperature......48 7...........3 Reaction with iodine .................................................................58 7.............78 11....................................................................5 Technical natural products ...................86 11.....................45 7 Release of water from the sample .....................1 Reaction with methanol.77 11.................................................1.3 Technical products – organic ..........2.........................................6 Determination using the drying oven ............

........92 12............92 12......................98 13...................METTLER TOLEDO Good Titration PracticeTM in KF Titration 12..95 12..........1 For samples soluble in methanol or ethanol ........................4.......................................93 12......................................4 For ketones and aldehydes........................................................................98 3 ....6...........................................91 12................................................95 12...............95 12................92 12.............................................................................1 For samples that are soluble in methanol or ethanol .......................96 12.....................98 13...2 Formula for the external dissolution .....................4...3 For samples insoluble in methanol or ethanol........4 Reagents and solvents for coulometric analysis ................................5 Water Standards for Karl Fischer volumetric titration.91 12...............................4...........................95 12........6...................2 Two-component reagent: ...............................98 13....................96 12..........................................................................................................1 Formula for the external extraction ...............94 12..............................6.....................................2 For samples poorly soluble in methanol or ethanol....................................................................98 13.........................6 Titrants and solvents for volumetric analysis ...........3 Reagents for coulometry: ...............6..............6.........................................................2 For samples that are poorely soluble in methanol or ethanol .........................90 12..................................................4 Safety data for the KF-components and auxiliary solvents: ...........1 One-component reagent ...3 Standards for Karl Fischer coulometry......5 For acids and bases (pH value) ..................................97 13 Hazards and waste disposal tips ...............................................5 For acids and bases (pH value) .....................................4................4........................................................4 For ketones and aldehydes...............3 For samples that are insoluble in methanol or ethanol .......93 12..............................

by G. DO185 Drying Oven for the DL18 Karl Fischer Volumetric Titrator. First microprocessor controlled KF titrator (METTLER DL18) with automatic drift compensation. promoted by publications by E. Introduction of the METTLER TOLEDO STROMBOLI KF Oven Sample Changer. Wernimont and F. M. and solvent dispensing and removal. 2000 2001 2002 2008 4 . Use of Karl Fischer method spreads. “Testing of mineral oil hydrocarbons and solvents: Determination of water content according to Karl Fischer . First German DIN standard for the Karl Fischer titration (DIN 51777. and DL67/70ES/77 Titrators Introduction of the METTLER TOLEDO DL31/DL38 KF Titrators with dedicated fuzzy logic control. D. 0.1 mg/g) with test certificate according to DIN 50049-2.0. 1959 1960 1970 1980 1984 1985 1989 1990 1995 1997 1998 New DV705 KF Titration Stand with very low drift value (< 2μg/min) for the METTLER TOLEDO DL53/55/58. 1. Water standards (10. Publication on stabilized single-component Karl Fischer reagent by E.Direct method”). Eberius [3]. Peters and J. DL37 KF Coulometer from METTLER TOLEDO. Publication: Coulometric Karl Fischer Titration by A. They replaced the DL18/35 KF Volumetric Titrators. First coulometric KF titration instruments are commercially available.3 First titrator (METTLER TOLEDO DL55) with online curves E = f(t) and V = f(t) for Karl Fischer titration. titrant specific standard parameters and LEARN titration.J.0. Meyer and C. Automatic KF titration instruments with piston motorized burettes.1 1935 1943 1950 1952 1955 1956 An historic overview Publication: "Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern" by Karl Fischer [1]. Introduction of less poisonous KF reagents based on ethanolic solution. Solid KF Oven Standards with water contents of 5. respectively.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1 Fundamentals of the Karl Fischer titration 1. Introduction of the METTLER TOLEDO Titration Compact Line V20/V30 and C20/C30 Karl Fischer Instruments. Introduction of the METTLER TOLEDO DL32/39 KF Coulometers (generating cell with and without diaphragm). Pyridine-containing two-component reagents and dead-stop titration instruments are commercially available. Publication: “The Dead-Stop End Point“. L. Improved METTLER TOLEDO DO307 KF Manual Drying Oven.Boyd [4]. April 1956. First fully automatic KF titration with laboratory robots (METTLER DL18 and ZYMARK). Pyridine-free KF reagents are commercially available. First diaphragm-less cell for coulometric KF titration. S.5% and 1%. Enormous spread of the use of KF titration. Jungnickel. METTLER TOLEDO RONDO Sample Changer with Karl Fischer Kit for automated KF volumetric determination. Hopkinson [2].

the reaction between iodine and water takes place in the stoichiometric ratio of 1:1. the more methyl sulfite is formed by the capture of protons. In the pH range 5. W. it only acts as a buffering agent and can therefore be replaced by other bases.e.5. but rather the methyl sulfite ion. and the faster the rate of the Karl Fischer reaction. all the sulfur dioxide is present as methyl sulfite. In order to achieve an equilibrium shift to the right. Karl Fischer used pyridine for this purpose. I2 + SO2 + 3 Py + H2O → 2.2 The Karl Fischer chemical reaction I2 + SO2 + 2 H2O → 2 HI + H2SO4 The water content determination is based on the reaction described by R. methanol not only acts as a solvent but also participates directly in the reaction itself. In an alcoholic solution. Barenrecht [7] on the subject of the Karl Fischer reaction have revealed that: • • Pyridine is not directly involved in the reaction. depends on the pH value of the medium (see graphics below) -d[I2]/dt = k • [I2] • [SO2] • [H2O] One possible explanation for the influence of pH on the reaction rate is that it is not the sulfur dioxide itself that is oxidized by iodine under the influence of water. described by the rate constant k. The rate of the Karl Fischer reaction. the reaction between iodine and water takes place in the stoichiometric ratio of 1:2: 1. Py•SO3 + H2O → 2 Py-H+I– + Py•SO3 – Py-H+HSO4 – Further studies conducted by J. Smith. In an alcohol-free solution. the 5 . it is necessary to neutralize the acids that are formed during the process (HI and H2SO4).METTLER TOLEDO Good Titration PracticeTM in KF Titration 1. I2 + SO2 + 3 Py + H2O → 2. Bryanz and Mitchell [6] formulated a two-step reaction: 1. At pH values above 8. This is formed from sulfur dioxide and methanol according to the equation: 2 CH3OH + SO2 → CH3OH2+ + CH3OSO2- The higher the pH of the solution. the maximum reaction rate is reached here and cannot increase further. C. i.. Verhoff and E. Methanol proved to be suitable as a solvent. Bunsen [5]: Karl Fischer discovered that this reaction could be used for water determinations in a nonaqueous system containing an excess of sulfur dioxide [1].5 to 8. Py•SO3 + CH3OH → 2 Py-H+I– + Py•SO3 – Py-H+CH3SO4 According to these equations.

pH values less than 4 and greater than 8 should be avoided in practice. 6 . Seubert [9] identified methylsulfite in KF solutions with the aid of IR spectroscopy and isolated and identified methyl sulfate as the secondary product of the KF reaction. for determination in ketones or aldehydes). Methanol should therefore always be present in the minimum required amount. you should adjust the pH value to the ideal range by adding buffering agents (for acids: imidazole. In 1988.METTLER TOLEDO Good Titration PracticeTM in KF Titration reaction rate increases due to side reactions between iodine and hydroxide or methylate ions. you can use other alkohols such as. Barendrecht [7] observed an increase in the titer with water contents greater than 1 mol/L. On the basis of this knowledge.g. diethylene glycol monoethylether) [10. Scholz resulted in the following reaction scheme being proposed for the Karl Fischer reaction [8]: 1. dimethylformamide) Studies by Eberius [3] showed that iodine and water react in the ratio of 1:1 if the percentage of methanol in the solvent is 20% or more. for instance.g. pungent pyridine. 2-propanol. methoxyethanol. and for bases: salicylic acid).3 • Consequences for practical applications Influence of pH on the Karl Fischer reaction Since the maximum rate of the Karl Fischer titration is in the pH range 5.C.g. If a methanol-free titrant has to be used (e. A. ethylene glycol monomethyl ether.g. This improves the titer stability. (RNH) · SO3 R + 2 RN + I2 + H2O This resulted in the general chemical equation: ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I E. This reagent not only replaced the toxic. Scholz developed a pyridine-free Karl Fischer reagent with imidazole as base [8]. Scholz was also able to confirm the existence of basic methylsulfite in methanol/SO2/I2 solutions during the titration. however.5 to 8. Experiments on the stoichiometry of the reaction showed that methanol can in fact be replaced by other alcohols (e. Studies by E. is not a serious limitation because the water concentration in the solvent is usually much less. but also facilitated faster and more accurate titrations because imidazole buffers in a more favorable pH range than pyridine. This. methanol) (e. • Influence of the solvent on the Karl Fischer reaction The stoichiometry (molar ratio of H2O:I2) depends on the type of solvent: Alcoholic solvent Non-alcoholic solvent H2O:I2 = 1:1 H2O:I2 = 2:1 (e. With acidic or basic samples. ROH + SO2 + RN 2. → → (RNH) · SO3 R (RNH) · SO4 R + 2 (RNH)I 1. and references therein]. this results in a more sluggish endpoint and higher iodine consumption. E. J. in a titration. • Influence of the water content of the sample on the Karl Fischer reaction The water content of the sample also influences the H2O:I2 molar ratio. ethanol. Verhoff and E.

1 mg/mL for samples with a water content of less than 200 ppm. The reagent is available in three different concentrations: 5 mg/mL for samples with a water content of 1000 ppm to 100%.1. Suitable for samples where water is present in trace amounts: 1 ppm .100% Coulometric Karl Fischer Analysis Iodine is generated electrochemically during titration.5% 2. i.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2 Volumetric and Coulometric Karl Fischer Analyses The determination of the water content according to Karl Fischer is nowadays performed by two different techniques: – – Volumetric Karl Fischer Titration. Coulometric Karl Fischer Analysis. 7 .1 Volumetric KF reagents 2. You can also use a methanolic solvent mixture specially adapted to the sample as the solvent. The drop in titer. The solvent is methanol. The reagent can be stored for approximately two years. where iodine is generated by electrochemical oxidation in the cell The selection of the appropriate technique is based on the estimated water content in the sample: Volumetric Karl Fischer Titration Iodine is added by a burette during titration.5 mg/mL per year in a sealed bottle.. dissolved in a suitable alcohol. the decrease in concentration. Suitable for samples where water is present as a major component: 100 ppm .e. is approximately 0. where a solution containing iodine is added using a motorized piston burette. 2 mg/mL for samples with a water content of less than 1000 ppm.1 One-component KF reagent The titrant contains iodine. sulfur dioxide and imidazole.

As a result. some manufacturers also sell the titrant separated into solution A (sulfur dioxide. Special methanol-free KF one-component reagents such as e. dissolved in an alcohol (usually methanol).METTLER TOLEDO Good Titration PracticeTM in KF Titration 2.1.g. favorably priced. from VWR/MERCK) are commercially available to prevent this problem. A titration speed two or three times as high can be achieved with the two-component reagent. 2. imidazole. The separation into titrant and solvent improves stability of the KF reagents. High titration speed. Note that it may be necessary to adapt the end point value in the titration method to these reagents. additional water is produced and titrated at the same time.g. which allow for fast and accurate Karl Fischer titrations. sulfur dioxide and pyridine.1. 8 .4 Special reagents for aldehydes and ketones Aldehydes (R-CHO) and ketones (R-CO-R) form acetals and ketals if titrated with standard methanol-containing reagents. The titrant has a stable titer.1. such as amines. Solvent capacity restricted. sulfur dioxide and 2-methoxyethanol. 2 mg/mL for samples with a water content of less than 1000 ppm. methanol). – Titer less stable. This special reagent is also suitable for substances that react with methanol. + Simple handling.2 Two-component KF reagent The titrant contains iodine and methanol. or an alcoholic mixture. e. whereas the solvent consists of sulfur dioxide and a base. To improve stability. methanol) and B (iodine. These solutions are mixed 1:1 just before use to form the one-component titrant. imidazole and methanol. from Sigma-Aldrich) and e. pyridine. reagents containing pyridine are still used because they are cheaper and can be made in-house.3 Pyridine-containing reagents Despite the existence of pyridine-free reagents. leading to higher water contents and a vanishing end point. Reagents One-component Two-component 2.g. Some manufacturers have slightly increased the pyridine content in the titrant to achieve a higher titration speed. The solvent contains sulfur dioxide. It is available in two different concentrations: • • 5 mg/mL for samples with a water content of 1000 ppm to 100%. stable titer. The solvent is either methanol or consists of methanol mixtures. Two-component reagent: The titrant contains iodine dissolved in an alcohol. increases their lifetime. provided that the bottle is tightly sealed. One-component reagent: The titrant contains iodine. Both the components are very stable in storage. imidazole. whereas the solvent contains 2-chloroethanol and trichloromethane. HYDRANAL® (Composite 5K and Working Medium K. One-component reagent: The titrant contains iodine. methanol. titration speed slower.g. e. and results in higher titration speed. The titration takes slightly longer than with the standard KF reagent. This reagent is declared as “rapid”. apura® (CombiTitrant 5 Keto with CombiSolvent Keto. dissolved in methanol.

The classical coulometric cell consists of two parts. 2.2. ethanol-based reagents were launched in 1998. The generator is close to the measuring electrode*. Both parts are separated by a diaphragm. These reagents also allow for titration of several ketones which form ketals considerably more slowly in ethanol than in methanol.1 KF coulometry Coulometric KF determination of water is based on the standard reaction equation for the KF reaction. whereas the solvent contains sulfur dioxide. * The terms "generator electrode" and "measuring electrode" mean an arrangement of two electrodes (anode and cathode) to form an electrolytic cell. or “inner burette”) incorporated into the glass titration cell. 9 . imidazole. which is monitoring the potential of the sample solution by voltametric technique during coulometric titration. a double pin platinum electrode.1. ROH + SO2 + 3 RN + I2 + H2O → (RNH)•SO4 R + 2 (RNH)I In coulometry.5 Karl Fischer reagents with ethanol Since ethanol is less toxic than methanol.METTLER TOLEDO Good Titration PracticeTM in KF Titration 2. two-component. the anode compartment and the cathode compartment.→ I2 + 2 e Iodine generation occurs at a generator electrode* (also called “generator cell”. however. diethanolamine and ethanol.2 Coulometric KF analysis 2. the iodine is generated electrochemically by anodic oxidation in the coulometric cell according to the following half-reaction: 2 I . The titrant contains iodine and ethanol.

are oxidized to one molecule of iodine. 2 I. imidazole and iodide salts. An ammonium salt is added to the catholyte in order to promote hydrogen production. as chloroform. CH3SO3H. This consists of sulfur dioxide. other solvents such e. the reagent that enables completion of the whole electrochemical reaction: the oxidation reaction in the anolyte compartment is completed by a reduction reaction in the catholyte compartment. i. This is the main product formed. To avoid this.→ I2 → H2O 10 . it is necessary to first recall the definition of 1 Coulomb: one coulomb. present in the anolyte compartment. C. This can cause the cathode to become black. I-.2 Stoichiometry of the coulometric KF rection The amount of water titrated by coulometric technique is determined by the amount of electrical current given in Coulomb. it is known that to produce one mole of a chemical substance that requires one electron. Depending on the application.g. the KF electrolyte which is required for the oxidation in order to generate iodine by applying a current at the generating electrode. the positive hydrogen ions are reduced to hydrogen.METTLER TOLEDO Good Titration PracticeTM in KF Titration The anode compartment contains the anolyte. iodine is generated from iodide by electrochemical oxidation. can reach the cathode where it is reduced to a sulfide compound (obnoxious smell!). is the quantity of charge that is transported by a current of 1 ampere in one second. Anode reaction At the anode. Note that methyl sulfonic acid. which subsequently reacts with water. Subsequently.e. i. 1C=1A·1s On the other hand. C. iodine reacts with water. Methanol or ethanol is used as solvent. or the same reagent as used in the anode compartment.→ H2 + 2 RN Ammonium ions are then reduced with the formation of hydrogen and a free amine. 96485 C of current are needed. 2. The negative iodide ions release electrons at the anode and form iodine. 2 [RN]H+ + 2e. releasing two electrons at the anode. the catholyte should be replaced once in two weeks. To calculate it. hexanol or ethylene glycol may be added. used to generate iodine. The value 96845 C/mol is known as the Faraday constant. Cathode reaction At the cathode. The catholyte is either a manufacturer-specific special reagent.2. I2. In Karl Fischer reaction two iodide ions.e. The cathode compartment contains the catholyte. octanol.

2.015 g/mol. it is strongly recommended that the coulometer is regularly checked by measuring a certified water standard.712 C electrical current. 2. this calculation can be expressed as follows: 1 mg of water corresponds to a consumption of 10.e. 2 x 96485 C/mol is required for 1 mole of water. it is used as a reference method for the determination of water content. At very low conductivities (i. etc. The maximum pulse height depends on the following factors: conductivity of the anolyte voltage at the generator electrode surface of the generator electrode The voltage at the generator electrode and the surface of the electrode depend on the type of coulometer.METTLER TOLEDO Good Titration PracticeTM in KF Titration Therefore. 200 and 100 mA. 2. less than 3–4 μS/cm).3 Iodine generation Iodine is generated by means of current pulses of 400. coulometry is designated as absolute method. The main advantages compared to cells with diaphragms are: no contamination or blockage of the diaphragm easier cleaning lower drift 11 . Since current and time can be accurately measured. the conductivity of the anolyte is influenced by the samples and additional solvents (chloroform. the maximum possible current applied by the instrument is 100 mA. As a consequence.2. hexanol.). For an electrochemically optimized Karl Fischer cell. 300. In addition. With standard conductivity values. the coulometer operates with current pulses of 400 mA.4 Generator electrode without diaphragm with diaphragm without diaphragm The first commercially available diaphragmless cell for KF coulometry was introduced in 1989. This gives an iodine generation rate which corresponds to a maximum of 2240 μg water/min. Nevertheless. For this reason. no standardization of the coulometric KF reagents is necessary. the current conversion efficiency for iodine production is assumed to be 100%. Since the molar mass of water is 18. The rate of iodine generation is adjusted by varying the pulse duration and frequency and the pulse height (in mA).

The diaphragmless cell is ideal for the determination of the water content of the following compounds: hydrocarbons .ethers ketones (with special reagent) . especially for nitro compounds such as nitrobenzene. especially when easily reducible. Note that hydrogen gas generated at the cathode is forming gas bubbles around its surface. may also be reduced at the cathode by the formation of water. 2. the cathode is a small-size pin). other easily reducible substances such as unsaturated fatty acids. Thus. R-NO2 + 3 H2 → R-NH2 + 2 H2O Besides this. and for very accurate determinations.edible oils petroleum oils A cell with diaphragm is required for: samples with a very low water content (< 50 μg water/sample) very accurate determinations nitro compounds unsaturated hydrocarbons. the cell with diaphragm may yield more precise results. Nascent hydrogen is formed at the cathode.e. this makes it almost impossible for iodine to reach the cathode and be reduced to iodide. In practice. This is a very good reducing agent.g. The cathode is smaller and made in such a way that iodine cannot reach the cathode (i. lower than 50 μg water/sample). In addition. a different geometry is used for the generating cell without diaphragm. However. To avoid this concurring reaction. This effect is further enhanced by the small dimensions of the cathode.. etc.5 Limitations for the use of the cell without diaphragm The cell without diaphragm is not suitable for samples that are easily reduced.2.phenols (most) esters . for measurement of samples having a very low water content (e. it is still possible for a very small amount of iodine to reach the cathode.METTLER TOLEDO Good Titration PracticeTM in KF Titration Originally. the generator cell was first built with a porous ceramic frit (diaphragm) separating the inner cathode compartment from the anode compartment. 12 . Nevertheless.acetamides etheric oils and essences .chlorinated hydrocarbons alcohols . The purpose is to prevent that iodine molecules generated at the anode are immediately reduced to iodide ions at the cathode instead of reacting with water. The latter can thus react more efficiently with water. a relatively high stirrer speed allows for more rapid distribution of the generated iodine molecules. the relative error due to this effect can be minimized by using a larger amount of sample.

the viscosity of the solution and its temperature.the termination of the analysis. constant AC current – the polarization current "Ipol" – is applied to a double pin platinum electrode. When the voltage drops below a defined value. A high voltage is necessary to maintain the specified polarization current at the electrode. there is no free iodine in the titration/anolyte solution. and the addition or production stopped exactly at the end point.1 Principle of bipotentiometric indication A bipotentiometric indication is used for the volumetric Karl Fischer titration as well as for the coulometric analysis (in electrochemical terminology this is also called "2-electrode potentiometry").the control algorithm and its parameters. and hence. . . Free iodine causes ionic conduction and the voltage needs to be reduced to keep the polarization current constant. A small. Ideally. Only then can the titrant consumption or the generated iodine amount be determined with the desired accuracy. there will be free iodine in the titration solution.the addition speed or generation rate of iodine . 13 . The resulting titration speed depends on the following factors: .the reaction rate of the Karl Fischer reaction . The control of the titration is only possible if the end point is indicated. the titration is terminated.the stirring speed and mixing of the sample solution. . 3. • • • As soon as all the water has reacted with iodine.1 Indication 3. • • As long as the added iodine reacts with the water. iodine should be added or generated as quickly as possible.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3 Titration control and end point determination The addition or generation of iodine must be controlled. the water content.1.

A voltage of ca. The iodine is present only at low concentration.the polarization current. This free iodine gives rise to "ionic conduction". Above all.(to a lesser extent) the type of electrode (i. respectively. i. I2. which are present in excess in the titration solution. 14 .e.e. this value depends on the polarization current. • • At the beginning and during the titration: As long as the iodine generated reacts with the water. again. The two negatively charged iodide ions are attracted by the positively charged platinum pin. the titration end point is reached if the potential at the polarized platinum double pin electrode drops below a specific predefined value.2 End point and polarization current The Karl Fischer titration is terminated when an excess of iodine is detected in the titration cell. Thorough mixing of the titration/anolyte solution is necessary in order to achieve constant "ionic conduction". . free iodine is present in the titration/anolyte solution. At the end of the titration: As soon as all the water in the sample has reacted with the iodine. If mixing is poor. Ionic conduction Iodine takes up an electron at the negatively charged platinum pin of the indicator electrode and is thereby reduced to iodide (I-). then releases the electron again at the positively charged platinum pin and is again oxidized to iodine. there is no free iodine in the titration/anolyte solution. It then acquires two electrons and turns into iodide ions (2 I–).METTLER TOLEDO Good Titration PracticeTM in KF Titration • The ionic conduction takes the following course: an iodine molecule is attracted by the negatively charged platinum pin. The end point value mainly depends on . geometry and dimensions of the metal parts) .the solvent or anolyte used in the instrument. Now a low voltage of 50 mV to 100 mV is required to keep the polarization current constant. This leads to a termination of "ionic conduction" and the measurement signal becomes unstable. 3. Iodide ions.1. This drop in voltage is used to indicate the end of the titration. Ipol . no iodine reaches the negatively charged platinum pin. 400 mV to 650 mV is necessary to maintain the set polarization current at the double pin electrode. where they donate the electrons and form an iodine molecule.

pin length: 3 to 4 mm. i.METTLER TOLEDO Good Titration PracticeTM in KF Titration For the volumetric KF titration. On the other hand. The condition of the sensor has an influence on the potential jump Platinum is a strongly adsorbing metal.e. Sensors with short platinum pins (< 3 mm). pin length: 3 . exhibit a larger potential jump and also a higher end point. a double ring or plates instead of rings. The larger the diameter of the pipe. on the other hand. e. the lower the pressure needed to transport the desired amount of water through the pipe (= smaller pressure difference). With use. and subsequently it remains constant. The current density can be compared to a water pipe where a specific water has to flow.4 mm. the following end points have been defined for methanolic one-component and two-component KF reagents using a V20/V30 volumetric KF titrator or T70/T90 Excellence titrator (double pin platinum electrode. The layer is formed during the first ten titrations.g. just after the equivalence point. This makes it more difficult to stop the titration at the right moment. exhibit a smaller potential jump. i. the polarization current should be set as low as possible. Sensors with a large platinum surface. With used sensors. this leads to a larger potential jump compared to a cleaned or a new sensor (without layer). Influence of the sensor The potential jump at the end of the titration is also influenced by the geometry (surface and design) of the platinum sensing material of the sensor. 15 . its surface can easily bond suitable chemical compounds. with longer pins.e. pin diameter: 1 mm): AC Polarization current / µA 24 Endpoint / mV 100 For the coulometric KF analysis. and increases the risk of over titration. In general the larger the platinum surface the smaller the current density. a lower polarization current gives a smaller and steeper potential jump at the end of the titration. However. As a consequence. a layer is formed on the surface of the platinum pin sensor. iodine excess should be as low as possible to get accurate results. and increases the sensor resistance. pin diameter: 1 mm): AC Polarization current / µA 5 Endpoint / mV 100 The same end point values can be used for ethanol based KF coulometric reagents. the following values have been obtained with a C20/C30 KF Coulometer (double pin platinum sensor. Which polarization current should be used? A higher polarization current requires a larger iodine excess (indicated by a pronounced yellow coloration of the titration cell solution) to achieve ionic conduction for the determination of the end point.

a large excess of sulfur dioxide is present in the solvent. 3. 2.0 mL In the coulometric KF analysis.3 Stirring speed and dispersion of the volumetric KF titrant Good mixing is essential for fast and accurate KF titrations. irregular. and the reaction rate also decreases: iodine must be generated or added more slowly because a small water amount is still present.the sulfur dioxide concentration. the titration may also be too slow. On the other hand. sulfur dioxide is present in large excess in the anolyte. lower reaction rates are achieved with anolyte solutions that have been used for a long time.5 . [I2] . the water content is high.0 mL 1. which gives a high reaction rate. It is consumed with each additional measured sample leading to a decreasing dioxide concentration. the pH value of the solution has a strong influence on the rate and in particular on the stoichiometry of the Karl Fischer reaction. Example (V20/V30/T70/T90): One-component reagent Two-component reagent 2-3 min with a titrant consumption of 2. stirring speed. Karl Fischer titrations with the two component reagent are thus significantly faster than with the one component reagent. Iodine generation or addition can proceed rapidly because iodine immediately reacts with water. In the volumetric KF titration.d[I2] / dt = k · [I2] · [SO2] · [H2O] In addition. [SO2] . the water concentration is lower.2 Reaction rate The reaction rate of the Karl Fischer titration depends on: . point of titrant addition (volumetric KF titration). note that sulfur dioxide is added only in slight excess with the iodine titrant solution when using one component titrant.and on the iodine concentration.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. As a consequence. [H2O] .the water concentration. shape of the vessel (volumetric KF titration).2 min with a titrant consumption of 2. and overtitration may occur. Mixing is influenced by the 1. 3. Iodine generation or addition is usually the rate determining factor. At the beginning. Stirring speed The optimum stirring speed is obtained when a distinct vortex is visible. with the twocomponent reagents. If 16 . This results in a reaction rate up to 2 times faster for the two component reagent than for the one component reagent. If the speed is too slow. Towards the end of the titration.

Otherwise the sensor may directly detect added iodine.METTLER TOLEDO Good Titration PracticeTM in KF Titration bubbles form into the solution. Furthermore. If a longer stirring bar is used. Iodine would not be distributed upwards. Bubbles falsify the measured values. turbulence is not achieved and the mixing effectiveness is lower. This is essential for a fast reaction rate and for short titration times. Point of titrant addition The titrant should be added where the turbulence is the greatest to ensure efficient mixing. but rather along the base directly towards the sensor. the point of addition should be sufficiently far away from the sensor to allow for sufficient time for reaction. the stirring speed is too fast. Vessel shape The conical shape of the beaker and the short stirring bar lead to turbulence at the point of titrant addition that effectively disperses the titrant. leading to slower addition and longer titration time. 17 .

The recommended standard values are listed in the following table: Recommended standard values Sensor Ipol [µA] Stirrer speed [%] End point [mV] Control band [mV] Dosing rate (min) [µL/min] Dosing rate (max) [mL/min] Start Driftstop relative [µg/min] 1-Comp titrant 24 35 100 400 80 5 normal 15 2-Comp titrant 24 35 100 400 100 3 normal 15 3. The following drawing reveals a schematical illustration of the control band: 18 .4 Control parameters in the volumetric KF titration Several parameters can be defined in the titration method in order to optimize the method for the samples and the reagents.1 The Control Band The control band is a modifiable control parameter for both types of KF reagents.4.METTLER TOLEDO Good Titration PracticeTM in KF Titration 3. Cautious The volumetric KF methods of the V20/V30 as well as T70 and T90 use KF titrant specific titration control parameters. An overview of the control parameters is given as follows: Volumetric KF Titration End point Control band Dosing rate (max) Dosing rate (min) Start: Normal. The dynamic behaviour of the control can be influenced by a variation of the control band.

4.METTLER TOLEDO Good Titration PracticeTM in KF Titration The titrant addition is calculated on one hand by using the distance of the actual potential from the end point and on the other by using dE/dt. You should select Start: Cautious for one and two component reagents if the amount of water in the sample is less than 500 µg. which leads to a stronger reduction of the dosing speed. With large amounts of water. Burette size [mL] 1 5 10 20 Maximum dosing rate [mL/min] 3 15 30 60 Remark: Since the maximum dosing rate of a 1 mL burette is lower than the standard parameter 5 mL/min in the case of a 1-Comp titrant. the titrator automatically issues a warning. In this case you can activate the Start: Cautious parameter. the titration starts so quickly that overtitration may occur. Recommendations 1. if the control band width is decreased.3 The Cautious start If the water content is very low. 3. if the polarization current changes. the titration will take too long. sensors with very short platinum pins (< 3 mm). Dosing rate (max) = 2 mL/min. i. at higher water contents. the control reacts more sensitively to potential changes. This is more suited for small water amounts. 3.4. The maximum dosing rate is dependent on the actual burette size.4 Polarization current and end point Each end point is valid for a specific polarization current. You can also set the maximum dosing rate to a lower value for small amounts of water if you wish the titration to progress more cautiously. The end point for a specific polarization current is influenced by the sensor and the solvent. In the cautious mode. The closer the potential to the end point. Thus. 2. longer titration times and poorer repeatability are resulting by selecting a higher end point potential value. e. In particular.4.The dynamics of the control can be influenced in the following way: Increase of the control band Aggressive control Smooth control Two different controls are used for 1-Comp and 2-Comp titrants.e. 19 . the slower is the titrant addition. The 2-Comp titrant control reacts more sensitively to a potential drop than the 1-Comp titrant control.g. In both cases (normal and cautious mode) the maximum dosing rate will be reached at the end of the ramping up.. the titration starts with a slower acceleration (ramp up) than in the normal mode. 3. The following points represent possible contributing factors: contaminated or old sensors. however.2 The minimum and maximum dosing rate Both rates limit the dosing speed of the titrant to an upper or lower level. the end point must be adjusted.

this results in an illdefined titration end point. In order to achieve a good repeatability. If 2-comp ethanolic reagents are used. The consequences of choosing a too low end point value are illustrated in the figures above: On the right side. Therefore the potential jump at the end of the titration is smaller compared to conventional reagents. the control band shall be decreased to 100 mV and the maximum dosing rate decreased to about 50%. Therefore it is recommended to decrease the polarization current to about 15 μA. • If Chloroform or Xylene is added in order to dissolve oil samples. the titration curve is more or less flat towards the end. 20 . e. the overall ionic conductivity is increased. setting up of the titrant as 1-comp KF titrant yields shorter titration times. the sensor current shall be reduced to 15 μA.4. the overall ionic conductivity is decreased. instead of methanol or ethanol. the maximum dosing rate can be set higher for certain reagents: 4 mL/min for Riedel de Haen 2-Comp 5. If one-component reagents are used. used as solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration - long alkyl chain alcohols.g. Ethanol-based reagents • Compared to the methanol-based reagents. the titration can be accelarated by reduction of the control band to 300 mV. Composolver E) the standard 1-Comp parameters (cf. Auxiliary reagents • If formamide is added to the solvent. This measure allows the system to cope with the reduced conductivity.5 Application tips Methanol based reagents • The standard parameters listed in the table above are ideal for the titration with methanol-based reagents.g. 3. 2-propanol. the system reacts slowly in the case of ethanol based reagents. • • If 1-Comp titrants are used with Ethanol (e. • If 1-comp titrants are used. up to 8 mL/min for most 2-Comp 2 titrants. table) work fine. • If 2-comp titrants are used. which will lead to long titration times and to low precision. This results in a lower voltage required to maintain the polarization current.

which is the case in 1-Comp systems. In most cases 300 – 400 mV are well-suited. E E t Oscillating system behaviour. There is no need to accurately adjust the control band to the actual start potential. 2. However the control band shall not exceed the start potential. In general.4. In the case of 2-comp reagents over titration can be prevented by reduction of the maximum dosing rate. The most straight forward influence on the control behaviour is achieved by a variation of the maximum dosing rate. which is the case in some ethanolic reagents. 2-methoxyethanol. 100 mA) 21 .5 Control paramaters in the coulometric KF Analysis An overview of the relevant control parameters is given as follows: End point Control band Rate: Normal.6 General recommendations 1. Cautious Generator current: Automatic. 3.METTLER TOLEDO Good Titration PracticeTM in KF Titration KF reagents for ketones • An end point value of 150 mV for both one-component and two-component reagents is recommended when using special KF reagents for aldehydes and ketones. the 1-Comp control is suitable for systems that show an oscillating potential behaviour. 3.g. ->Use the 1-Comp control Smooth system behaviour ->Use the 2-Comp control t 3. This control is also recommended for 2Comp systems that show a noisy signal at the beginning of the titration. If the titration takes too long. 200. The minimum dosing rate shall be used to fine tune the final phase of the titration. where the methanol has been replaced by e. Fix (400. an increase of the control band is recommended. Furthermore it is recommended to reduce the polarization current to a value of 15 μA. 300.

300. Variation of pulse length (time). the slower is the generation of iodine. i.e. absolute drift stop. Five termination parameters can be defined in the titration method: delay time.e.25 µL for a 5 mL burette). minimum titration time 22 .METTLER TOLEDO Good Titration PracticeTM in KF Titration The iodine generation rate in the C20/C30 Coulometric Compact Karl Fischer Instruments depends on the distance from the end point. 3. Initially. The coulometer provides two different modes for iodine generation under the control parameter “Rate”: 1. as soon as the was potential value was lower than the set end point during the defined delay time. pulse frequency and pulse height (mA) are used as variables by the instruments.g. the pulse height can be automatically changed by the system if in the titration method the control parameter “Generator current” is set to “Automatic”.. iodine is generated by means of current pulses of 400. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA.e. high resolution burettes (0. In addition. maximum titration time. Later on. This parameter shortens the titration time and leads to repeatable results. and improved KF titration stands (i. the iodine generation is higher than in the cautious mode. it has been possible to reduce the delay time to 5 to 10 seconds due to the introduction of • • • new. 200 and 100 mA. the slope of the iodine generation is steeper and the rate is increased based on the measured potential value. tightly sealed stand). i. Since the first developed KF reagents reacted slowly. Normal: This iodine generation mode is generally used for all water content determinations.e. then the titration was stopped. relative drift stop. The fixed setting is used for solutions that exhibit a difficult characteristic with respect to conductivity. The iodine generation starts slowly. i.6 Termination parameters for both coulometric and volumetric KF titration The KF titration can be terminated using various parameters. Cautious: Suitable for samples of low water content (e. The closer the measured potential value from the predefined end point is. the slope of the iodine generation rate is flat at the beginning of the titration. During the course of the titration it increases up to the maximum rate at a generating current of 400 mA.Fix). pyridine-free reagents with a faster reaction rate. More specifically. a delayed switch-off time of 10 to 20 seconds was set at the end point. In particular. 2. or it can be set to a specific value (“Generator current” . less than 50-100 μg water per sample). the online determination of the drift during analysis has enabled a so-called "drift stop" to be used as a termination parameter.

Disadvantage: The minimum rate must be adapted to the initial drift and the titrant concentration. otherwise the termination criterion is never satisfied.Maximum titration time The titration is terminated after the defined time.e. 23 . 10 µg/min (volumetric) • Advantage: Independent on the titrant concentration. Disadvantage: The value optimized to the initial drift. The smallest increment must be sufficiently large to compensate the drift. has to be t/s • Relative drift stop The titration is terminated as soon as the actual drift drops below the sum of the initial drift (i. . the absolute drift stop value must be greater than the initial drift. easy to understand (volumetric). 5-15 μg/min (volumetric) • Advantage: independent on the initial drift.m the drift before titration) and the relative drift. Typical absolute drift stop value: 3 µg/min (coulometric). Typical delay time: 5 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Delay time The titration is terminated when the potential remains below the end point for a defined time (e.g. Typical value for the relative drift stop = 2-5 μg/min (coulometric). otherwise the termination criterion will never be reached. After the defined time has elapsed. especially if working with the KF sample oven. 15 s) following the addition or generation of iodine. the titration is terminated and the result is printed. Absolute drift stop Termination occurs as soon as the actual drift drops below the predefined absolute drift value.15 seconds (Coulometric/Volumetric) • • Advantage: well-known method. titrant concentration (volumetric) and side reactions. • Advantage: This parameter ensures a high repeatability of the results. Thus.

Thus.6. Maximum titration time for determinations with the KF drying oven When using the drying oven. this is the simplest and most universal parameter to use. • Advantage: This parameter ensures a high repeatability of the results. This termination parameter is also well-suited when the internal extraction is needed to determine the water content in insoluble sample: The water contained in insoluble samples is extracted during the titration.Minimum titration time Titration is not to be terminated before this time in [s] is reached (exception: the maximum volume has been reached). The vaporization of water is also irregular in the final stages. the following values are recommended for volumetric KF titration: One-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. the drift at the end is often greater than the initial drift. so 24 . The final traces are only extracted very slowly. This parameter is independent of the the initial drift (coulometric. Two-component reagent: A relative drift stop value of 5 to 15 µg/min is an optimum value for achieving good repeatability. This is particularly critical in connection with the "slower" reagents for ketones and aldehydes. and the titrant concentration (volumetric). A relative drift stop of 20 to 40 µg/min shortens the titration time without affecting the repeatability. you can ignore these traces.. 3.e. but involves a risk that the titration will be terminated a bit too early.METTLER TOLEDO Good Titration PracticeTM in KF Titration . possibly resulting in poorer repeatability and lower water contents. If the water content is relatively high. The value of the relative drift stop influences the repeatability and the titration time: • • Drift stop (low value) → better repeatability poorer repeatability → → long titration time short titration time Drift stop (high value) → In particular.1 Using and optimizing the termination parameters for both volumetric and coulometric KF titration The following termination criteria are most commonly used for water determination by Karl Fischer titration: Relative drift stop for trouble-free. you can terminate the titration at a higher drift (relative drift stop = 40 to 70 µg/min). It is recommended to be used for substances that release water slowly. volumetric). A relative drift stop of 20 to 30 µg/min shortens the titration time. Use the drift/time curve to determine this value. The reason for this is either a very slow release of the last traces of water or a slow thermal decomposition of the sample. i. soluble samples You should normally choose the relative drift stop as a termination parameter.

METTLER TOLEDO Good Titration PracticeTM in KF Titration that the repeatability of the titration termination using the drift stop parameter is poor. If the drift stop value is not reached. If the drift is greater than 10 µg/min. Relative drift stop/maximum titration time for problematic samples Some samples lead to a high drift value at the end of the titration. 25 . Note: To obtain accurate and reliable results you should only work with the coulometer when the drift is lower than 10 µg/min. (Set the minimum titration time equal maximum titration time). This is the case with samples that only release the final traces of water very slowly or that produce side reactions. The higher drift is therefore influenced to a large extent by the sample. you should take measures to reduce the drift. the titration is terminated at the latest after the defined maximum time. It gives you the best accuracy and repeatability of results. A combination of the relative drift stop and the maximum titration time has proved effective for such samples. the maximum titration time has proven to be best termination criterion in practice. Therefore.

The total moisture can be titrated more quickly by gently moving the vessel from side to side so that solvent swirls up the side of the vessel to pick up moisture adsorbed on the glass walls. The drift. The air within the titration vessel also contains moisture. where the relative humidity can achieve values of more than 80%. The factors include: • • • • the atmospheric humidity the working medium the pH of the sample the side reactions between the sample and the Karl Fischer reagent 4. there will be moisture on the glass surface of the titration cell and the inserts.1 Titration stand The titration stand must be sealed as tightly as possible against atmospheric moisture. Silica gel can be regenerated over night at 150 °C. The drying capacity of the desiccant is limited and it depends on the humidity and can be exhausted after 2 . The desiccant absorbs the moisture and protects the titration cell against the ingress of moisture. it is titrated to dryness during pretitration. The following rules should be observed: • • Close all openings in the titration stand.4 weeks (indicated by a colour change of the indicator of the silica gel). After the anolyte (coulometer) or the solvent (volumeter) has been added. whereas molecular sieves require temperatures up to 300 °C. This problem is particularly relevant in tropical climates or in coastal regions.1. the higher the atmospheric humidity in the laboratory. Do not shake too vigorously to avoid solvent gets on the cover of the vessel. however. i. the greater is its influence on the results of the Karl Fischer titration. The assumption that air-conditioned rooms have a lower atmospheric humidity is often not true: the majority of air-conditioning systems simply cool the air.3 hours. However. • Protect the titration cell with a desiccant (3 Å molecular sieve and silica gel). The air-conditioning system should therefore be equipped with a moisture condenser. This can take 1 . remains high because the moisture present on the glass walls and the air in the titration cell diffuse only slowly into the anolyte (solvent).METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. since cold air cannot absorb as much moisture. Moisture can enter the sample. When you assemble the titration stand for the first time.1 The influence of atmospheric humidity (drift determination) Atmospheric humidity represents the most relevant source of error in Karl Fischer titration. In this way.e. 26 . the titrant and the titration stand. until it is absolutely free of water. Briefly. The Karl Fischer titration Various factors must be taken into account with Karl Fischer titration to obtain correct results. The Karl Fischer titrator should never be installed close to a ventilator of the air conditioning system! 4. the relative humidity increases. the residual moisture dissolves more rapidly into the anolyte (solvent). Condition the titration cell before use.

traces of water will always find a way into the titration cell.(drift * titration time). it is necessary to quantify the amount of water entering the titration cell during titration. it is also possible to use the value of a previously performed drift determination (“Determination”). For accurate results. In the standby titration. Therefore it must be taken into account when calculating the water content.1. the last measured drift value is automatically stored. the drift value should therefore be as low as possible and stable before the start of a titration! 27 . and its value is displayed on the screen. On the other hand. On the other hand.2 The drift No titration stand is completely water tight. t. the drift indicates the quantity of water that enters the titration stand over a defined period. the KF titrator continuously titrates the water that diffuses into the cell. or a fixed value can be defined into the titration method (“Fix value”). and is given in μg water/minute.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. This is achieved by titration of the dry solvent for a defined time (drift determination). In this respect. At the start of a sample titration. if it is defined as the parameter “Source for drift: Online” in method function “Titration stand (KF stand)”. or it can be entered by the user (“Request”): Source for Drift Online Determination Fix value Request Explanation Last measured value of standby The drift is determined and stored as raw result DRIFT A fixed value is defined into method The value can be entered immediately after starting sample titration The drift value is subsequently used in the calculation of the result in order to compensate for the moisture that entered the titration cell according to the following formula: Sample result = Total amount of water determined . Therefore. this water amount is also titrated during analysis.

the moisture enters the diaphragm and is slowly released into the anode compartment. when the drying oven is used.Pour approx.2. 3 . the levels slowly become the same. 2. the anolyte should be topped up from time to time with anhydrous methanol. the level of the anolyte drops due to evaporation. a flow occurs from the cathode compartment to the anode compartment. . By ensuring that the level of the anolyte is higher than the one of the catholyte. 5 mL from the bottle with a syringe and inject it into the generator electrode or empty an ampoule of catholyte into the generator electrode. As soon as the stirrer is switched off. .The generator electrode should dip approx. which leads to a higher drift. This can be avoided as it follows: 1.Make sure that the level of the anolyte is approx.First transfer 5 mL catholyte to the cathode compartment. Normally this brown coloration disappears on filling the titration cell because the iodine excess is consumed. . The catholyte can be dehydrated with a few drops of a volumetric KF one component titrant. you must add some methanol or sample so that the color changes to yellow. 100 mL electrolyte solution (anolyte) into the titration cell. Note: In production. Higher anolyte level → low drift Lower anolyte level → drift is high . some anolyte solutions contain an excess of iodide and the solution has a brown colour.5 cm into the electrolyte solution. 28 . the level of the anolyte increases. If the level of the catholyte is the same or higher.Take approx.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. However. . • Titration cell with diaphragmless generator electrode .Then fill the anode compartment with approx.1 Filling the coulometric cell • Cell with generator electrode with diaphragm .The difference in level between the anolyte and catholyte is maintained as long as the stirrer is in operation. 2. The catholyte always contains traces of water. 100 mL anolyte.5 mm higher than that of the catholyte.2 Working with the coulometric KF instruments 4. If this is not the case. In this case. .When a sample is injected into the anode compartment.

In the cathode compartment sulfides and mercaptans are formed that lead to an obnoxious smell and a higher drift.Anolyte solutions (100 mL): after 1000 mg water. . .2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. It is fully controlled by the titrator. The higher the level in the anode compartment.g. below 10 μS. when using a generator electrode with diaphragm. it is common use to replace both the anolyte and catholyte at the same time If after adding samples. This can happen if large amounts of samples of low conductivity are titrated. The working principle of the Solvent Manager is illustrated in the following schematical illustrations: 29 . the worse the stirring efficiency will be. Any contact with the reagent is avoided during draining and refilling of the titration cell.Catholyte solutions (5 mL): after 200 mg water. the drift slowly increases. After being used for two weeks. The capacity is monitored by the coulometers (see operating instructions). With poorly soluble samples. the dissolving capacity of the anolyte (coulometric KF) is exhausted and an emulsion is formed. and the risk of over titration increases. This can lead to wrong results. e. If an emulsion forms in the anode compartment. The Solvent Manager is located on top of the waste bottle and includes strong air pump (diaphragm pump) and an electromagnetic valve. A level sensor in the waste bottle prevents from overflow. If an electrolyte is used for a long period without replacement.3 Secure draining and filling of the titration cell: SOLVENT MANAGER The easiest and secure way of draining and filling the coulometric titration cell is performed with the external KF liquid handling device Solvent Manger. • • • • • 4. In practice.2 When do you have to replace the electrolyte? The electrolyte must be replaced in the following situations: • If the capacity of the electrolyte is exceeded. If the drift is too high.2. the level of the solvent or the anolyte exceeds the 150 mL mark. If the conductivity of the anolyte drops to a very low value.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 1a: Put the draining and reagent refill tube into the coulometric titration cell. Step 1b: Start the reagent replacement either from the manual function ‘Replace reagent’ or from a predefined Shortcut on the Home screen of the Touchscreen. 30 . Step 2: The Anolyte is drained into the waste bottle by applying vacuum.

Step 4: After a predefined time or by manual interaction the pressure within the solvent/anolyte bottle is relieved by switching the magnetic valce into the initial position.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 3: The pump direction is switched by activation of the magnetic valve and subsequently fresh solvent is pumped into the titration cell by applying over pressure of dry air. Depending on the type of the generator cell the following liquid handling actions can be performed: Diaphragmless generator cell: Replacement of the anolyte Generator cell with diaphragm: Replacement of the anolyte and draining of the catholyte 31 . In this configuration only draining of the titration cell is possible. The Solvent Manager is part of the standard delivery of the C20 and C30 Compact coulometric KF titrators. drying tube and tube holder enables both draining and refilling. An optional reagent exchange set consisting of tubes.

. It provides the following: Monitoring three reagent parameters Usable life in days Capacity in mg water Number of samples When due. especially if dirty samples are analyzed. • Thorough cleaning of the generator electrode If the generator electrode and the diaphragm are strongly contaminated.Afterwards dry the generator electrode at a maximum temperature of 50 °C in an oven or with a hot air dryer. The generator electrode with diaphragm must be cleaned periodically because contamination accumulates in the diaphragm over a longer period of time. Place the empty generator electrode in the chromic acid or fill the generator electrode with chromic acid and let it flow through. Methanol flows through the diaphragm and rinses out moisture and contaminants. The C30 provides a reagent monitoring routine which is called Reagent Control. The procedure is identical to that described above.Fill the generator electrode with anhydrous methanol.4 Cleaning the coulometric KF titration cell The titration cell and both electrodes should be cleaned. the most effective cleaning agent is chromic acid. Afterwards dry the vessel at 100 °C in an oven or with a hot air drier. reagents can be replaced directly out of running method Choice of enforcing the user to replace it immediately or ask again later 4. • 32 . Method B: . Moisture and contaminants are rinsed out of the diaphragm. . which leads to a higher drift. Simple cleaning and drying of the generator electrode Method A: .Methanol flows through the diaphragm into the cathode compartment.2.This procedure should be repeated at least once. Drying is not necessary if you use it immediately. . Afterwards thoroughly rinse the generator electrode with water.METTLER TOLEDO Good Titration PracticeTM in KF Titration Note: The tubes for anolyte exchange are not left in the titration cell during titration. The contaminants can originate from samples or are side products that have been formed in the cathode compartment by reduction. since it would cause a higher drift value.Place the empty generator electrode in anhydrous methanol. • Cleaning the titration vessel Clean the titration vessel with water or a suitable solvent. then with anhydrous methanol and dry it as described above. If immediate use is required rinsing with anhydrous methanol shall be applied.

a layer is formed on the platinum surface after the first few titrations. A significant change in temperature may occur: The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably with temperature. This test of the complete system by a titer determination is therefore an essential condition for accurate. a weekly titer determination would be sufficient (the concentration of the one-component titrant changes by 0. 3. 4.if the desiccant on the titrant bottle is "used up".METTLER TOLEDO Good Titration PracticeTM in KF Titration 4. The Ohmic resistance of the electrode is increased.2. • Clean the platinum pin with a paper tissue. samples may be deposited on the surface of the electrode. The titrant is not chemically stable. The titrant may absorb moisture from the atmosphere reducing its concentration (the anhydrous methanol in the titrant is very hygroscopic) . so that there is a sharp drop in concentration. • With heavily contaminated electrodes.if the titrant bottle is not tightly sealed. .3. The volumetric KF titrators enable monitoring of the usable life and life span of the titrant. 2) Connect the S7 connection of the generator cell with the indication electrode.3 Volumetric KF Titration: Titrant concentration The titrant concentration can change due to the following reasons: 1. the measuring electrode must be cleaned. A reminder can be set to warn the user at the start of every titration that the usable life is about to expire in the predefined time range (days). In this case. 2. The tightness of the titration stand and the proper functioning of the burette and the end point indication are also checked at the same time as the concentration is determined. This leads to a higher potential jump. 4. the tightness of the titrant bottle and the desired level of accuracy. which prevents a good indication. However.5 Cleaning the measuring electrode Generally. This is sufficient in most cases. As already described. place the electrode in 0.5 mol/L sulfuric acid. We recommend to determine the titrant concentration daily. Based on the chemical stability of the titrant. it is better to determine the concentration every 2 to 4 hours. 3) Stop the method when the cleaning is finished so that the polarization current at the indication electrode is stopped.g. The layer should therefore not be removed by cleaning. In countries where the temperature varies considerably during the course of the day and the lab is not air-conditioned. the one-component titrant.1 How often should the concentration be determined? How often the concentration is determined depends on the choice of titrant. and let an electrical current of about 400 mA flow across the platinum pins for 60 s by starting the KF titration: 1) Disconnect the S7 connection of the indication electrode. e. In the global settings within the setup menu of 33 . This also becomes noticeable through a dark coloration of the anolyte at the end point. repeatable results. while the two-component titrant is rather stable).01 mg/mL per week. the indicating electrode does not need cleaning.

3. Determine the weight by back weighing and enter it as sample size. i. Since it slowly dissolves in methanol. Either the user is simply warned or the usage of the expired titrant is blocked. This sample size yields an optimum titrant consumption of 1. - 34 . i.using the same titration stand with the same volume of solvent. Mix for 3 minutes to achieve complete dissolution before you start the titration. which prevents the execution of further titrations.and at the same temperature.e. you should first grind it to a fine powder before using it or use special Di-sodium tartrate dehydrate for Karl Fischer Titration Procedure . Note: 1. thus the titrant concentration slightly but continuously decreases slightly when left to stand for a long time.e.66% of water. 2. Na2C4H4O6•2H2O (M = 230.Use the optimized METTLER TOLEDO method M301 Weigh between 0.2 Concentration determination with di-sodium tartrate dihydrate General Di-sodium tartrate dihydrate.5 mL with a 5 mL burette.METTLER TOLEDO Good Titration PracticeTM in KF Titration the titrator actions can be defined that will be applied if the usable life or life span is actually exceeded.08 g di-sodium tartrate dihydrate with the aid of a weighing boat.08 g/mol). 26-50 % of burette volume. Add it into the titration vessel. it contains 15.: .3 to 2. 4. Under normal conditions. Determine the concentration under the same conditions as for sample analysis.04 and 0. The plastic tubing is not absolutely water vapor-tight. Make sure that nothing adheres to the beaker wall or to the electrode. is the primary standard for Karl Fischer titration since it is stable and non-hygroscopic. . Rinse the burette 2 times into a waste bottle before you determine the concentration.

Partially soluble. The values that are obtained are approx. Partially soluble. mixing time 1 minute. You can only perform one determination in 50 mL of 1:1 mixture (with 0.0 mg/g General Water standards consist of a mixture of organic solvents containing a specific amount of water.5 g of water standard 10.3 Concentration determination with Water Standard 10.0. You must either change the solvent after every sample or use pure Solvent* for the determination. always take into account the limited solubility of di-sodium tartrate dihydrate in the most commonly used solvents for Karl Fischer titrations: In Solvent* Highly soluble.0 to 1. The values obtained are approximately 10% too high. They are thus protected against the ingress of moisture and can be stored for up to five years.05 g di-sodium tartrate dihydrate).e.045 g di-sodium tartrate). Thus. mixing time 1 minute. mixing time 1 minute. You can perform six determinations in 30 mL of Solvent* before you need to change it. Less soluble. "HYDRANAL®-Water Standard 10. Slightly soluble. You cannot perform more than one determinations in 40 mL of ethanol (with 0. A cloudy solution will falsify the results (i. In Solvent*/chloroform mixture 1:1 or Solvent*/decanol mixture 1:1 In Solvent*/formamide mixture 1:1 In methanol In methanol/chloroform mixture 1:1 or methanol/decanol mixture 1:1 In methanol/formamide mixture 1:1 In solvent for aldehydes and ketones (one-component reagent) In ethanol *Solvent: solvent for the two-component reagent 4. You must perform the determination in pure methanol! Highly soluble.g. This content is confirmed by the test certificate enclosed with every package. 30% too high. too high titer). Procedure To achieve an optimum consumption of 2 to 3 mL titrant with a concentration of 5 mg/mL.0" from Sigma-Aldrich® with 10 mg water in 10 g standard. You must perform the determination in pure methanol! Less soluble. Highly soluble. You can perform eight determinations in 40 mL of this mixture before you need to change the solvent. mixing time 5 minutes. mixing time 2 to 3 minutes.05 g di-sodium tartrate). you should weigh in 1. The water standards are supplied in glass ampoules. You cannot perform more than three determinations in 40 mL of methanol (with 0. 35 . mixing time 2 to 3 minutes.METTLER TOLEDO Good Titration PracticeTM in KF Titration Solubility of di-sodium tartrate dihydrate Di-sodium tartrate dihydrate must be completely dissolved (clear solution!) to obtain correct results. e.3.

Glass syringes are better.g.01 g as the sample size. A balance with a resolution of 0. Rinse a 10 mL syringe with approximately 1 mL of water standard. Plastic syringes may introduce a small amount of moisture.0 mg water/g for a titrant concentration of 2 or 1 mg/mL.0 µL deionized water with a 10 µL syringe. accurate results. Open the ampoule shortly before the measurement in accordance with the enclosed instructions. Thus. To reduce the influence of the atmospheric moisture. 4. METTLER TOLEDO XP205 balance) or with a 10 or 20 µL precision syringe (e.1 mg does not satisfy the requirements for a repeatable titration. Start the titration without any mixing time. You can use a water standard with 1. the whole content of the ampoule is completely drawn into the syringe. This is due to the very small amount of sample (10 to 20 µL) that has to be injected. 6.METTLER TOLEDO Good Titration PracticeTM in KF Titration – – – – – – Notes 1. Use a new ampoule for each new concentration determination. Enter 0. Inject 1 to 1. Procedure – – You should weigh between 10 and 20 µL of deionized water or water according to ISO 3696 to achieve a consumption of 2 to 4 mL titrant with a concentration of 5 mg/mL.g. with a Hamilton microliter syringe). the water content is increased and thus this will falsify the results. The error is minimized by rinsing and conditioning the syringe beforehand. Draw the whole content of the ampoule into the 10 mL syringe. or with a 10. 3.3.01 mg (e. – – – 36 . it is strongly recommended determining the concentration either with di-sodium tartrate dihydrate. Use the METTLER TOLEDO method M300 The water standard is highly soluble in all commonly used solvents for Karl Fischer titration and can therefore be used without restrictions.4 Concentration determination with pure water General When using pure water to determine the concentration. The sample should be weighed either using a balance with a resolution of 0. a very good deal of practice and precise working is required to obtain repeatable. The content of an ampoule is sufficient for 3 to 5 determinations. 2. 5. Start the titration without any mixing time.0 mg/g water standard. Determine the weight by back weighing.5 mL at a time as an aliquot. Inject exactly 10. 4. In an open ampoule the liquid standard is exposed to air moisture.

massage oil. transformer oil. - 4. All the screws in the syringe must be tightened securely. emulsions Petrochemical products: crude oil. corn. if it is absorbent. it may draw water out of the needle!). Adjust the plunger to exactly 10. suppositories Sugar products: jelly.3. ethereal oils Petrochemical products: gasoline. the largest part of the solvent mixture must always be an alcohol (most preferably methanol) to ensure that the Karl Fischer reaction is strictly stoichiometric. Insert the syringe through the 1 mm hole of the three-hole adapter. 2. Only freely available water undergoes reaction with the Karl Fischer reagent. to avoid touching the glass part. Always add each sample in exactly the same way. potato chips Chloroform Decanol Octanol Hexanol Dodecanol Toluene Formamide 70% 50% 50% 50% (30%) 37 . kerosene Pharmaceutical products: ointments. dioxane. salicylic acid Foods: honey. jelly bears Starch products: flour. Do not warm the syringe. However. You can get rid of any bubbles in the syringe by expelling the water rapidly. You should always observe the following points when determining the concentration with a 10 µL syringe: Precondition the 10 µL syringe for approximately one hour by filling it with water. diesel oil. lay it down on the adapter and empty it completely. It is possible to determine the titrant concentration with water in all the solvents commonly used for Karl Fischer titration. You can use mixture of solvents to achieve complete dissolution. Hold the syringe at right angles directly in front of your eyes to read off the value. yogurt. Solvent Methanol Max.0 µL.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. hydraulic oil. amount 100% Samples Solvents: toluene. tar products. Always use a syringe with a long metal shaft. beverages Cosmetics: soaps. ester Organic products: urea. creams. After setting the volume. noodles.5 The solvent To determine the water content in a sample. wipe off any drops that have adhered to the needle with two fingers (be careful if you use a paper towel. caramel. the sample must release water completely. alcohols. fatty creams Waxes. fat Oils: edible oil.

Sugar is the only type of sample that dissolves in formamide. 3. If exhausted. the water will no longer be completely released.salicylic or benzoic acid for basic samples. 2.3. Once again.6 Dissolving capacity of the solvent The dissolving or extraction capacity of the solvent is a crucial factor in Karl Fischer titration. 4. The solvents that are used should contain as few water as possible (< 100 ppm). or the titration will take too long and titrant will be wasted. or by indicating the maximum number of samples to be titrated. the titration of subsequent samples will then be very slow. The extraction capacity can be improved by increasing the temperature (e. In this case. or the stoichiometry of the Karl Fischer reaction will change and the results will be wrong. too low water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration Notes 1. If acidic or basic samples are titrated. it is necessary to replace the solvent timely. The amount of formamide at 50 °C should not exceed 30%. and .g. 50°C). The titrator accumulates the total water amount continuously during titrations and reports "Solvent capacity exhausted" as soon as the specified value is exceeded. On the other hand. The Compact Line KF titrators are able to monitor the solvent capacity: the user can define when the solvent should be replaced by specifying the usable life.e. the amount of water in mg which has been titrated.imidazole is used for acidic samples. 38 . starch products will not dissolve in it. you must replace the solvent timely. Therefore. which may be completely expended if you titrate a large number of samples with high water content. This will lead to incorrect results. formamide effectively extracts water from starch products. i. The solvent for the two-component reagent contains SO2. buffering agents are first added to the solvent to ensure that the titration is quick and without side reactions: .

5. 2. If you have to store the sample. The sample should be taken quickly to exclude. you should take into account the following points: 1. 3. Substances with very low water content: Substances with a very low water content are frequently extremely hygroscopic. The sample must be representative. 5. i. the water is not uniformly dispersed. such as butter. water may be separated from the sample if it is left to stand for a long time. Heterogeneous water distribution in samples: In non-polar liquids. or at least minimize. you will no longer be able to determine its true water content. oils. 4. With liquid samples that do not dissolve water such as oils. it must contain the same average amount of water as the material as a whole. This can happen when a sample cools and the water solubility is decreased. "An analysis cannot be better than the actual sample!" When sampling. It floats on the surface or sinks to the bottom. 39 . keep it in a tightly sealed bottle: Glass bottles are preferable to plastic bottles because plastic is not completely gastight.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5 Sampling 5. Hygroscopic solids may exhibit higher water content on the surface than inside if they have absorbed atmospheric moisture during storage. Use a bottle with an optimum volume for the amount of sample: the smaller the gas space above the sample.1 Taking the sample When taking samples for water determination. With liquid samples. you must be extremely careful to exclude atmospheric moisture .the most common source of error.g. Use sample bottles with small openings to minimize the ingress of moisture. In such cases. rinse the bottles two or three times with the sample beforehand.e.2 Storing the sample After you have taken the sample. In the case of non-polar solids. Liquids of this type must be thoroughly mixed (by shaking) before a sample is taken. you should determine its water content as soon as possible. If the water content of a sample changes during sampling due to moisture being absorbed or desorbed. the solubility of water in the sample can be increased using a solubility promotion agent such as 2-propanol. Use bottles with a septum stopper for liquids of very low water content. the absorption or release of moisture. which cannot be mixed as thoroughly as liquids. The sample must therefore be taken very quickly and with a syringe or a spatula that is absolutely dry. and thus air moisture can penetrate the plastic and absorbed by the sample. the lower the amount of moisture. e. the sample should be larger the more heterogeneous the distribution of the water.

For optimum accuracy with determinations in the range from 1 ppm to 1% water. the accuracy is improved if larger sample amounts are used. Water content determinations below 1000 ppm are not required to be quite as accurate: a relative standard deviation srel of 1 to 5% is generally considered as acceptable for such values. A titrant consumption of 0.01 10 8 0. In general. Under optimum measurement conditions. it is recommended to use the minimum sample size given in the following table: Water content Min. the accuracy increases with the amount of sample. This corresponds to 0.0 10000 = 1% 0.0 1000 1 1. and the required accuracy and precision.5 to 17.3 Amount of sample The amount of sample used depends on • • the expected water content. a KF titrant with a lower concentration (1 or 2 mg/mL) has to be used.5 mg water per sample for a 5 mL burette with a titrant concentration of 5 mg/mL.2 1. the optimum amount of water is approximately 10 mg per sample. the amount of sample should require a titrant consumption between 30 and 70% of the nominal burette volume. and the following minimum sample sizes should be used: Water content Min.05 mL is thus still acceptable when using a 5 mL burette. Repeatable results can be obtained even with 0. If a high level of accuracy is required.1 to 0.05 mg water per sample with a titrant concentration of 1 mg/mL.08 50 5 0.1 1. sample size [ppm] [g] 10 8 50 7 100 5 200 4 500 3 1000 2 40 .25 100 4 0.0 For volumetric titrations.METTLER TOLEDO Good Titration PracticeTM in KF Titration 5.1 mg water per sample. This corresponds to 7. For coulometric analyses. approx. because the absorption of air moisture during sampling and sample addition becomes less important. the optimum amount of water is in the range from 0. For a more accurate determination of water traces (10 ppm to 1000 ppm) by volumetric KF ttiration.4 500 2 1.1 to 0. 10-50 μg water can be detected if the demand for repeatability is not too high. As a rule of thumb.0 5000 0.5 to 2 mg water per sample. sample size Amount of water [ppm] [g] [mg] 1 10 0. because the absorption of atmospheric moisture during sampling or sample addition becomes less important.

Logarithmic scale! 41 . 1 mg for coulometric KF) or the recommended range The optimum point is connected by a straight line to the expected water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration Determination of the amount of sample for a water content in the range from 1000 ppm to 100% Principle: The recommended sample size can be determined as a function of the expected water content for optimum KF analysis. The intersection point of this line with the "Amount of sample" scale represents the recommended amount of sample to be used. Procedure: • • • Note: Start from the optimum point (10 mg for volumetric KF.

42 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Example: Expected water content: Optimum amount of water: Optimum sample amount: 5000 ppm 10 mg/sample 2g The Compact volumetric and colometric KF titrators support the user with a sample size calculation routine. which is accessible in the online titrations screen: Dependent on the expected water content. an optimum sample weight range is recommended.

Inject the sample using a 5 or 10 mL syringe with a thick needle into the titration cell. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. 50 °C and fill it into a syringe. paraffin. hydraulic oils. silicone oil. Rinse a 10 mL syringe 2-3 times with the sample Inject the sample using a 1 mL or 10 mL syringe through a septum cap. you can use a syringe without needle since the sample can be added via the larger hole of the three-hole adapter. The syringe is heated together with the wax. benzene glycerol. especially with samples of low water content. In the case of a volumetric Karl Fischer titrator. Store the sample in a bottle with a septum stopper to avoid moisture absorption from the air. alcoholic beverages methanol. creams. This prevents the sample from solidifying in the syringe during the weighing. aqueous emulsions. Possibly warm the sample slightly to lower the viscosity.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6 Sample addition 6. The following procedures are suitable for the different types of liquid samples: Sample characteristics High water content Low viscosity Examples perfumes. suppositories b c Liquefy the sample in an oven at approx. honey a Waxy candle wax. ski wax. Inject it into the cell using a wide-bore needle. you must take suitable precautions to prevent atmospheric moisture from being absorbed. 43 . Low water content Low water content Hygroscopic Viscous Very viscous ointments. toluene. edible oils hexane. mineral oils massage oil Procedure Inject the sample into the titration vessel either through a septum (KF coulometer) or through the needle hole in the three-hole adapter (volumetric KF titrator) using a 1 mL syringe with needle. yoghurt. Fill the 5 or 10 mL syringe with sample after removal of the piston. In the case of a volumetric Karl Fischer titrator.1 Liquid samples When adding liquid samples.

Replace the syringe with the remaining sample on the balance and back weigh it. the drop will adhere to the septum. Fill a syringe without a plunger with molecular sieves. use bottles with a septum stopper and pressure equalization. Withdraw the plunger so that the drop at the tip of the needle is sucked back into the needle. To avoid this. Sample addition of liquids with the back weighing technique – Fill the syringe to a quarter with sample. Otherwise when the syringe is removed. you must aerate the bottle with dry air (equalize the pressure). seal it with cotton wool and insert it into the septum bottle using a short needle. a vacuum develops in the bottle with septum stopper and it will no longer be possible to take a sample aliquot. Start the titration method by pressing the <Start> button Inject the sample into the titration cell through the septum stopper. If the sample is hygroscopic or has a low water content (< 1000 ppm). Empty the syringe (into the waste bottle) and repeat the rinsing two or three times. Withdraw the plunger and rinse the syringe with the sample by shaking it. Start the titration.METTLER TOLEDO Good Titration PracticeTM in KF Titration Taking samples from a bottle with septum stopper After several samples have been taken. Fill the syringe with sample and wipe the needle with a paper tissue. – – – – – – – – – – 44 . Enter the sample size in the titrator or transfer it automatically. Air flows through the molecular sieve into the bottle when you take a sample aliquot. Place the syringe (upside down) in a beaker on the balance pan and tare the balance to "0".

this would lead to an error of 5% to 10%. salts. chocolate. The sample should be quickly weighed and added to minimize air exposure.g. e. e. Sample characteristic Brittle Hard/soft Pourable Procedure e.g. jellied fruits. fatty e. jelly bears. – Add the sample with a weighing boat. the storage of samples in a refrigerator may cause water to condense. in a volumetric KF titrator solids can be directly transferred into the titration vessel.g. other methods have to be used for the determination of low water content by KF coulometry in solid samples: • • • External extraction External dissolution Drying oven On the other hand. about 50-100 μg water enter the anode compartment. Finely powdered Dusty Finely powdered with very low water content Soft – Use a weighing boat with an attached flexible tubing to add the sample: it prevents the sample from adhering to the wall of the titration vessel or to the electrode. it is necessary to warm up such samples to room temperature in a closed vessel before weighing. almond paste: Cut into small pieces with scissors or a knife and add the sample with a spatula. depending on the ambient humidity. If possible. crystalline samples: Weighing boat – Grind hard. With an optimum sample size of 1 mg water/sample.2 Solid samples It is not possible to directly titrate solid samples using KF coulometry . thus. salicylic acid. cooled analytical mill.when the titration cell is opened to add the sample. 45 . Hard. it should be added under the same conditions as it was transported and stored. cellulose powder: – Either weigh the sample in a dry box or extract it externally.g. pulverize less hard samples in a mortar. solid fat: – Grate the product and add the sample with a spatula. For this reason. coarse-grained samples in a closed. For instance.METTLER TOLEDO Good Titration PracticeTM in KF Titration 6.

to prevent the sample from adhering to the vessel wall or to the electrode. Add the sample into the titration vessel. ski wax. Do not use a syringe. Weight of solid samples with the back-weighing technique Weigh the sample in the weighing boat. honey. sugar products – The METTLER TOLEDO Visco-Spoon™ simplifies the handling with creamy samples since it can be directly mounted into the titration stand. margarine.METTLER TOLEDO Good Titration PracticeTM in KF Titration Soft. fatty. The syringe is heated up together with the wax.g. - 46 . edible fat: – Homogenize the sample well: the water is heterogeneously distributed. – Add the sample with a spatula. candles. Enter the weight in the titrator or transfer it automatically. because the water is released if it is pressurized Waxy e. 50 °C and fill them into a syringe. Back-weigh the empty weighing boat. This prevents the sample from hardening inside the syringe during the weighing process Creamy Highly viscous e.g. suppositories: – Liquefy the samples in a drying oven at approx. Start the titration. The water content is often lower atthe surface than inside the sample. Use a weighing boat with attached flexible tubing if necessary. paraffin. Tare the balance to zero. inhomogeneous e. chocolate cream.g. butter.

jellied fruits. e.g. Fibrous natural products Suspensions 47 .g. berries: Reduce with a homogenizer in an external solvent. This is not the case with solids if the water is bound as.g.g. fatty Soft. fatty Mince the product. sausage. it is necessary to crush insoluble solids in order to gain access to the trapped water.g. e.g. pharmaceuticals Water Example: Food Example: Gypsum (Ca2SO4 * 2 H2O) Thus.: • • • • entrapped water water of crystallization (salts). e. almond paste (“marzipan”): Cut into small pieces with scissors or a knife. hard salts: Grind in a closed. vegetable juices: Reduce with a homogenizer. solid fat: Grate the product. noodles.g. then reduce it further with a homogenizer in an external solvent.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7 Release of water from the sample Karl Fischer titration is only possible if the water in the samples is freely available. in plants) Water Example: Sugar. suitable sample preparations and special Karl Fischer methods are necessary to release water in these samples.g. e. brittle Viscous Hard. organic salts. cooled analytical mill. Sample preparation Water: Example: Biological samples First of all. dried fruit and vegetables. chocolate. The following methods are available: Sample characteristic Very hard Procedure e. e. crystalline products: Pulverize in a mortar. coffee beans: Crush in a mixer. cheese: Hard. inorganic salts. minerals. e. fruit juice extracts. meat.g. water adsorbed on surface capillary bounded water (e. brittle Moderately hard. grain.g. e. e.

grinding the sample additionally with a built-in homogenizer (see photos below).5 8.2 1.3 2. sugar.8 1. Water is then extracted providing the mixing time defined in the titration method is sufficiently long. heating the solution with a thermostating titration beaker.4 0. You can speed up the extraction of water from the sample by • • In many cases.1 4.4 1. Thermostatable vessel High–speed homogenizer Examples: Sample Flour Potato chips Ground hazelnuts Chocolate Instant coffee Dried chives Dried tarragon Aspirin Sweetener tablets Optical bleaching agent Result / % 12.8 Solvent Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Formamide:methanol 2:3 at 50 °C Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol / Homogenizer Methanol 48 .8 4. etc. using either methanol or a mixture of it as the solvent. potato chips.0 7.1 mg/pc 3. e.1 Internal extraction Internal extraction is suitable for insoluble solids that release water quickly when crushed: – – Add the crushed samples into the titration vessel.5 1.9 srel / % 0.3 1.4 1.g.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7.1 1.8 1. hazelnuts.0 1.9 0.9 0. the homogenizer eliminates the need to use auxiliary reagents such as formamide with.

pepper. shaking bath) placing the solution in an ultrasonic bath for a certain time or reducing the sample further with a built-in homogenizer. Provide sufficient solvent for the blank value determination so that enough solvent is available for the extraction. sugar and starch products for sugar (surface water) The organic solvents most commonly used are: • chloroform The external extraction is carried out in four steps: Step 1: Blank value determination of the extraction solvent Solvent in septum bottle Take a solvent aliquot Water content determination of solvent = blank value B - The water content of the solvent must be much less than the one of the sample. Pay attention to the water capacity of chloroform (max. The extraction of water can be improved • • • by shaking the solution (mechanical shaker. Briefly. 600 ppm). the finely crushed sample is added to a solvent with very low water content and is left to stand until the water has been released from the sample. edible fat) for natural substances (almonds. methanol decanol / octanol formamide for insoluble organic solids for fatty and dairy products (butter. curry) for dehydrated products for sugar (total water). 350 ppm) and toluene (max.2 External extraction External extraction is suitable for insoluble solids that release water only slowly when crushed as well as for samples with an extremely inhomogeneous water distribution. In particular. water is extracted from the sample by means of a defined quantity of solvent of known water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. butter milk. 49 .

Shaking is the method generally used for extraction. Step 3: Extraction - Shake. Add a sufficient amount of sample. the addition of dry quartz sand has proven useful for improving and speeding up the extraction. - 50 . The larger the sample. or use an ultrasonic bath with heating. A dilution factor of 10 . A mechanical shaker is normally used because the extraction time is often long (at least two hours or overnight). For the extraction of tablets. or use a homogenizer.METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 2: Weigh in solvent and sample Weigh solvent in = msolv Add sample Weigh sample = mext - Cut the sample into small pieces so that it releases its water more quickly and efficiently. the smaller the relative error because the total error is calculated with respect to the sample size.20 is normally used.

51 . take an aliquot and titrate Allow to settle Take an aliquot of the extraction solution Titrate sample The following equations are used to calculate the water content of the extracted sample: ⎛ msol B ⋅ msol ⋅ ⎜C ⋅ − ⎜ mext mext ⎝ ⎞ ⎟ ⎟ ⎠ For % : R (%) = 100 100 − C For ppm : 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − R( ppm) = 6 ⎟ mext ⎠ 10 − C ⎝ mext Water content in the sample P (% or ppm).METTLER TOLEDO Good Titration PracticeTM in KF Titration Step 4: Allow settling. Amount of solvent (g) Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) The detailed calculations which lead to these formulas are given in the appendix. Water content of the supernatant extraction solvent (% or ppm) %: C = (VEQ*CONC-TIME*DRIFT/1000)*0.1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m . R: C: B: msol: mext: m: Note: Blank value (water content of the solvent. % or ppm).

The weight of the solvent (msol).4 0.9 11.4 4. the weight of the sample (mext) and the weight of the aliquot of the supernatant solution containing the extracted water (sample size m) is entered into the respective sample data fields: 52 .3 0. The METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator are available with optimized method parameters for immediate execution.5 0.4 0.8 54.5 9.3 0.5 Decanol:formamide:methanol 8:2:1 Decanol:formamide:methanol 8:2:1 Decanol:formamide 1:1 Decanol:formamide:methanol 8:2:1 Methanol Methanol Formamide There is a dedicated KF method type ‘External Extraction’.2 Chloroform Volumetric KF Titration Sample Result / % srel / % Extraction solvent Cheese Liver sausage Mustard Chicken broth Tobacco Wool Acrylic paint 27.6 72. The solvent blank is determined directly from the method running in standby by pressing the ‘Start blank’ button.6 61.6 0.METTLER TOLEDO Good Titration PracticeTM in KF Titration Examples for the external extraction: KF Coulometry Sample Result / ppm srel / % Extraction solvent Sucrose (surface water) 72 4.4 0.

The water content of the solvent should be as low as possible. 2. the formula is automatically given. Note: 1. “External extraction”) in the method function “Calculation”. In particular. Chloroform. reaches the saturation limit for water already at 350 ppm! 53 .METTLER TOLEDO Good Titration PracticeTM in KF Titration The equation for the calculation of the water content of the extracted sample is predefined in the calculation method function.e. The amount of sample should be sufficiently large to ensure that the amount of water in the sample is significantly greater than that in the solvent prior to extraction. The amount of sample should also take account of the absorption capacity of the solvent. in order to maximize the extraction effect and ensure that the difference between the water contents before and after extraction is as large as possible. 3. for instance. by selecting the appropriate calculation (i.

3 formamide methanol methanol methanol chloroform The method corresponds to external extraction except that the sample dissolves completely in the external solvent. the addition of methanol is not necessary. ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % AND ppm: R: C: Water content in the sample P (% or ppm) Total water content (sample + solvent).2 1.8 2. The following solvents are commonly used: • • • • methanol formamide chloroform toluene for organic solids for sugar products for petroleum oils and adhesives for tar.3 External dissolution External dissolution is defined as the complete dissolution of a sample in a defined amount of solvent of known water content.2 10.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. %: C = (VEQ*CONC-TIME*DRIFT/1000)*0. or with a very low water content. External dissolution is suitable for soluble solids with an extremely inhomogeneous water distribution. only the calculation method function has to be adapted to by selecting the corresponding calculation from the list of proposed results. ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%. or with a high water content Pure solvents can be used to dissolve the samples. waxes and suppositories Example: Sample Result / ppm srel / % External solvent Sucrose (total water) Naphthalene Phenol Salicylic acid Contact adhesive (“Rubber cement”) 533 35 174 116 278 4.9 5. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent Weight of the sample aliquot (g) 54 .1/m ppm: C = (VEQ*CONC-TIME*DRIFT/1000)*1000/m B: msol: mext: m: Blank value (water content in % or ppm) of the solvent. The dedicated method type ‘External Extraction’ and the METTLER TOLEDO methods M305 for the volumetric KF titrator and M394 for the coulometric KF titrator can be used as templates. in % or ppm.

Remove approx. foodstuffs) in septum bottles means that external extraction or external dissolution as described in the previous sections are not recommended. the blank value correction is too large compared to the amount of water in the sample. You should therefore proceed as it follows: Take an aliquot of anolyte Inject it in the septum bottle Shake Take aliquot and titrate Procedure: 1. 6. Determine the weight by back weighing. If the solid has a low water content (<200 ppm). 5.METTLER TOLEDO Good Titration PracticeTM in KF Titration To obtain accurate results a large sample amount is used for substances with an inhomogeneous water distribution. 7. 7. this error is reduced. KF coulometry is not suitable for samples with water contents of 10-100% because a very small amount of sample would have to be used. weigh it and inject it into the septum bottle. Rinse the syringe two or three times in this way. and too much titrant is consumed.g. Determine the weight of anolyte injected by back weighing. because a large sample amount leads to a too long titration time. Draw 10 . 2. the sample is previously diluted through external dissolution to be able to titrate a larger sample aliquot. biological tissue. Draw an aliquot into the same syringe again. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension.20 mL of anolyte titrated to dryness into the syringe. serum. 3. 4. the error obtained by direct titration if the titration stand is opened to add the sample is too large. the error as a result of opening the titration stand will be between 10 and 30 µg.4 Lyophilized substance in septum bottles The extremely low water content of freeze-dried substances (e. weigh it and inject it into the titration cell. On the other hand. In fact. Direct titration is not suitable. If 1 g of sample has a water content of 100 ppm (= 100 µg) for instance. 55 . Thus. Since you are able to work with larger amounts of sample when working with this technique.

2. 4. If you know the lyophilized sample amount in the septum bottle. In this way. 10 mL of anolyte titrated to dryness from the titration cell using a 20 mL syringe with a long needle and then return it to the titration cell. Remove approx. because the anolyte titrated to dryness has a blank value of "0". The accuracy of a plastic syringe is enough. 8. 7. the final result must be multiplied by 4 (factor f = 4). 3. Alternative procedure: 1. 5. Shake the bottle or place it in an ultrasonic bath for 5 minutes so that the lyophilized substance dissolves or forms a suspension. Draw exactly 5 mL from the septum bottle into the same syringe again and inject it into the titration cell. neither the calculation for the external extraction nor for the external dissolution are needed for this procedure using the volume instead of the mass. zero must be entered for the blank value (B).METTLER TOLEDO Good Titration PracticeTM in KF Titration If the sample is completely dissolved: use the method type “External extraction” and the calculation for the "External dissolution" If a suspension is formed: use the method type “External Extraction” and the calculation for the "External extraction" Note: In both cases. Rinse the syringe two or three times in this way. then you can additionally calculate the result can be given in ppm. 56 . the water amount in the septum bottle is 4 times larger. Draw exactly 20 mL of anolyte titrated to dryness into the syringe and inject it into the septum bottle. The water amount in µg is determined. Since ¼ of the total amount was injected. 6. With a standard method calculation and calculate the water amount in µg. Thus.

Stop the gas flow after 1 to 2 mL titrant has been consumed. The gas must be directed through a water-dissolving. 57 . .When titrating large quantities of gas in the same solvent. . evaporated methanol lost in the gas stream must be replaced depending on titration time and number of determinations. .Add a sufficient amount of buffer solution into the titration vessel to determine the water content of acid gases such as e. .Adjust the gas stream to a constant flow rate with the control valve: 50 to 200 mL/min. Notes .METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. water-free absorption liquid in which CO2 itself does not dissolve. The water content in ppm is calculated by entering the volume and the density. the gas must be directed through the titration vessel for a defined period of time.Purge the sample vessel and the tubings thoroughly beforehand with the gas. Three-way valve Flow meter Gas Control valve The flow rate has to be constant to determine the volume necessary to calculate the water content: gas volume = gas flow rate x time.Purge the system with the gas before you start the determination. you should titrate the gas sample directly from the source. time" and a "Delay time" of e. The water contained in the gas is then absorbed by the liquid and can be determined by means of Karl Fischer titration in a process similar to external extraction.g. Determination .Calculate the volume from the time and the gas flow rate. . . If not.g. . . to ensure that the titration is terminated after the maximum time.If possible. you must fill the gas either into special gas sample tubes or into small steel cylinders. depending on the water content of the gas.Select "Max. hydrochloric acid.5 Determination of water in gases To determine the water content of gases. Sampling/sample addition .As soon as the drift is stable again. start the titration and reset the three-way valve to its original position in order to direct the gas into the titration vessel.With sample vessels the gas amount gas can be determined by differential weighing. . .Turn the three-way valve. 600 s as termination parameters.CO2 gas can not be titrated directly since iodine reacts with CO2. to prevent the gas from flowing into the titration vessel.

11 mg/L nitrogen gas from a cylinder: 1. chapter 7.6. that release water very slowly. 150 mL/min is ideal for DO308 and 70 mL/min for Stromboli (automated KF drying oven. the purge gases must be first dried before entering the KF oven. The water is transferred to the titration cell in a current of dry inert gas (purge gas).6. and the amount of water is determined. Thus. Air should therefore only be used for non-oxidizable.9 166 99.2 Purge gas Air contains oxygen. The purge gases commonly used contain moisture.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. which could react with the sample at higher temperatures.6 Determination using the drying oven This method is suitable for solids and liquids that 1. 58 . 7. the oven temperature should not exceed 160 °C. 7. If you use nitrogen from a gas cylinder. Experiments with various gas flow rates yielded the following results: Gas flow rate Recovery [mL/min]: [%]: 108 99.6.7 500 97. If you use air for organic samples. you should use a two-stage pressure regulator so that the final pressure is in the range 0. for accurate results do not select a too high gas flow rate.: o o air with 50% humidity: approx.1 bar (cf.g.5 .4 – 8. inorganic samples.6. causing the water in the sample to vaporize.0 mg/L Therefore. e.1 - The recovery rate is clearly decreasing with increasing gas flow rate.1 Principle The sample is heated in an oven. the residual moisture in the purge gas should be less than at least 10 μg/L (for coulometric determination) and 20 μg/L (for volumetric KF titration) in order to obtain accurate and repeatable results.4) A gas stream of approx.5). chapter 7. cause side reactions with the Karl Fischer reagent. For Karl Fischer titration. cf. or 2.

2. whereas molecular sieves requires temperatures up to 300 °C. in contrast to other desiccants. To ensure that the determination is repeatable. It is therefore recommended to dry the gas with a combination of silica gel and molecular sieves. In the case of KF coulometers. In order to avoid the latter you may also use the minimum time as termination parameter. you should set the maximum titration time as the termination parameter (i. deactivate the drift stop).80 µg H2O/L 40 .6. The amount depends on the gas flow rate and the type of KF reagent present in the titration cell. The short mix time is necessary so that a delayed vaporization of water does not lead to premature termination of the titration. all the water is vaporized and transferred to the titration cell. P2O5 KF one-component reagent Silica gel Molecular sieves 3 Å 50 . With some samples the drift at the end of the titration is significantly higher than the initial drift.3 Procedure There are two different methods to perform a KF titration with the drying oven: 1. Passing the gas stream into the titration cell causes the anolyte (in the KF coulometer) and solvent (generally methanol in KF volumetric titrator) to vaporize. Method 2: The water is first vaporized and then titrated afterward During a defined long mix time. i. 100% Phosphorous pentoxide.50 µg H2O/L 15 – 20 µg H2O/L 50 – 60 µg H2O/L 5 – 10 µg H2O/L 10 – 15 µg H2O/min 8 – 10 µg H2O/min 3 – 4 µg H2O/min 10 – 12 µg H2O/min 1 – 2 µg H2O/min You can use the following desiccants to dry the purge gas: – – Molecular sieves are the best drying agent as far as residual moisture is concerned. the titration starts and the released water is continuously titrated. Silica gel can be regenerated over night at 150 °C.e. they are rapidly exhausted. The relative drift stop or the maximum titration time can be used as the termination criterion. Method 1: The water evolved is continuously titrated After a short mix time (20 . Silica gel and molecular sieves have the advantage that they can be regenerated. At the end of the titration.e. In such cases you should use the maximum titration time as termination parameter (i. Start off with the silica gel to absorb the bulk of the water and then use molecular sieves to reduce the residual moisture to a minimum. but their water absorption capacity is low. the vaporization is often very irregular. there are two types of anolyte solutions: 59 .METTLER TOLEDO Good Titration PracticeTM in KF Titration Several agents are available to dry the purge gas: Method Residual moisture Residual moisture for 200 mL/min gas flow rate (drift) Sulfuric acid. especially methanol. The KF titration is then started. deactivate the drift stop).60 s). This is caused by a slow release of the final traces of water or slow thermal decomposition of the sample. 7.e. Silica gel is appreciably better in this respect.

The recovery therefore depends on the amount of methanol vaporized and the method used. The DO308 oven is equipped with a gas drying unit with two bottles for silica gel and molecular sieve. Coulomat AG Oven): Anolyte loss at 150 . fibers) or with samples of low water content. As an example data from coulometric determinations are indicated here below: Method Anolyte Gas flow rate Recovery / % 1 1 2 2 Coulomat AG Coulomat AG Oven Coulomat AG Coulomat AG Oven 166 mL/min 183 mL/min 166 mL/min 106 mL/min 99. the recovery is not 100%.5 . time Max.95 98. dedicated anolyte to be used with a KF Oven (e. time 60 . time Max.e. Examples: Sample Result / ppm No. as well as a gas flow meter.4. time Max. oven temperature 200 °C: approx. of samples srel / % T /°C Time/min Comments Polyamide Polyethylene Motor oil Cement Cooking salt Carbon black 5547 68 842 8200 360 3583 6 6 6 6 5 5 0.6. i.g. Due to the vaporization of the methanol. 3. you should replace the anolyte lost through vaporization with new anhydrous methanol.9 2.METTLER TOLEDO Good Titration PracticeTM in KF Titration – Standard anolyte solutions containing methanol (e. there is a small loss of water. This is particularly important with low-weight samples (e. time Max. i. Make sure that the level of the anolyte does not fall below that of the catholyte (higher drift!).1 Briefly: The less methanol is vaporized.g.2 1. 1 mL/hour – From time to time.200 mL/min. and the better the recovery.2 99.g. An air pump is available as an optional accessory.8 6.9 9.e.7 99. Coulomat AG or CombiCoulomat frit): Anolyte loss at 150 .200 mL/min.4 Manual Karl Fischer drying oven The METTLER TOLEDO DO308 drying oven can be operated in a temperature range from 50 to 300 °C.2 4. The procedure for the determination of water content is described in the operating instructions. oven temperature 200 °C: approx. 7.5 mL/hour Anolyte containing ethylene glycol.5 190 280 140 300 300 200 15 10 15 20 10 15 Max. It has a large glass sample boat capable of holding up to 10 cm3 of sample. time Max. the faster the water is titrated.

10. you may use the SIGMAALDRICH HYDRANAL® water standard KF oven 5.55% or VWR/VWR/MERCK water standard KF oven 1%. do not select the parameter "Auto start". If the drift is constant. the evaporated solvent lost in the gas stream has to be replaced. you should proceed as follows: 7.7%. 3. start the titration so that the drift value is automatically entered. To check the performance of the titrator/drying oven system. 2. The drift should be 5-10 μg H2O/min at a gas flow of 150 mL/min. If the drift is higher than 15 μg H2O/min. Always start the titration before you place the sample in the oven to ensure that the correct drift value is adopted by the method (online drift). Coulometer KF: The internal drying tube of the generator electrode has to be replaced with an external. Close the stop cock and purge the "hot zone". Set a gas flow rate of 150-200 mL/min. The evaporation is reduced by adding ethylene glycol (higher boiling point) to a maximum solvent ratio of 20-30%. For the same reason. If the water is titrated as soon as it begins to evaporate.5 to 4 mL/h for an oven temperature of 200 °C and a flow rate of 200 mL/min. A large amount of evaporated water cannot be fully absorbed by the solvent. and does not drop into the cathode compartment/ titration cell. This can happen when the titration is started only after complete evaporation. Some samples require some time before water starts evaporating. bent drying tube. . Open the stop cock. Experiments using methanol as the solvent gave a recovery rate of 98% for a stream of 166 mL/min. Some samples have surface water that is lost as soon as the oven is purged with dry gas. the recovery increases to 99. This leads to a too low result. 4. 61 9. For instance. In such cases. evaporated solvent does not condense in the drying tube. in volumetric KF titration the methanol loss is approx. If several determinations are performed in the same solvent. 5. Add the sample through the tapered joint and slide the glass boat with the sample into the oven: Guide rod with magnet Slider Glass sample boat 8. 6. 3. replace the silica gel and molecular sieves of the gas drying unit. Then. purge the "cold zone". Here a short mixing time (15 to 60 s) or the minimum titration time should be defined to prevent the titration from being terminated too early. and/or replace the anolyte of the KF coulometer.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments: 1.

The drying oven can be operated in the temperature range from 50 to 300°C. are included in the titration method.5 STROMBOLI automatic oven sample changer The METTLER TOLEDO STROMBOLI oven sample changer is a drying oven for automatic Karl Fischer titration with the KF Compact Volumetric V30 and Coulometric Tititrators C30 as well as with the Titration Excellence Titrators T70 and T90. After the analysis. The blue rubber cap seals the sample vial tightly against the oven. 62 . The oven heats the sample to the set temperature. 3.6. the lift is moved downward and gravity facilitates the removal of the sample vial from the oven. The purge gas flows through the sample vial and the water vaporized is transported via the transfer tube into the titration cell of the coulometer. Besides 14 places for glass sample vials. STROMBOLI is completely controlled by the titrator: all the parameters for the determination. while a glass tube pierces the aluminum foil cover. 2. 1 During a sample series: 2 3 1. The sample vials are moved upward into the oven by a lift. including the oven temperature.METTLER TOLEDO Good Titration PracticeTM in KF Titration 7. STROMBOLI offers one fixed place on the sample rack for an empty sample vials in order to determine the drift value.

fibers) or with samples of low water content.METTLER TOLEDO Good Titration PracticeTM in KF Titration Sample vials: Rubber cap Aluminum foil Sample vial The glass sample vials have a large volume (up to 25 mL). To determine the drift value accurately. The drift value is defined as the moisture entered into the titration cell by the purge gas. The sample vials are sealed with self-sealing aluminum foil and a rubber cup. Drift determination: The drift determination is performed with an empty vial on the first position of the sample rack.g. the moisture in the empty sample vial has first to be removed. This is particularly important with light samples (e. This takes 10-20 minutes as can be seen in the following diagram: 63 .

If. i. 64 . several blank value determinations can be performed one after the other in the same loop and the mean value calculated from the results. Performing the drift and blank value determination In general. The new blank value is automatically used for the blank correction. Multiple sample series at different temperatures Several series can be started on the same sample turntable – even at different temperatures.g. moisture in the sample vial. for example. they can be measured at different temperatures using the same method.e. The blank value can also vary as a function of temperature. drift value x time). If this is the case. This means that the stored drift value of the previous determination will be used. the silica gel and molecular sieves in the bottles of the gas drying unit can be replaced. at the end of a series the blank value can be measured again and compared with the value determined at the beginning. These method templates are based on a dedicated KF method type called ‘Stromboli’. The optimum blank value is in the range of 70 . In this case. you can enter the number of samples the series includes for each loop. and the adsorbed moisture on the glass walls of the vial) minus the amount of water due to the drift (i. By performing a drift determination at the end of the series or between several series. The blank value should be determined before each series because the humidity can change. The loops run through one after the other and the samples are processed sample for sample. Nevertheless. To determine the blank value as accurately as possible. At the start of the method. There are dedicated METTLER TOLEDO multi-loop methods available in the V30 (M313) and in the C30 (M396).e. a blank value determination should be performed before each series of samples since the ambient conditions (humidity. different plastic samples have to be analyzed. a drift determination should still be performed at least once a day in order to check whether the drift is too high (e. the vial used no longer has the same properties as the "fresh" sample vials.300 μg water. whose optimum bake-out temperatures differ.e. It is therefore not necessary to perform a drift determination before each series. gas flow.METTLER TOLEDO Good Titration PracticeTM in KF Titration Blank value determination: The blank value is the amount of water contained in an empty sample vial (i. the method contains a so-called sample loop.) are always slightly different. If the maximum titration time is used as termination criterion in the method -which is what we recommend. the drift value can change with time. one with the same properties as the sample vials into which the samples have been filled in). the blank value determination also takes the actual drift into account. the moisture in the air present in the vial. it is important to use a new sample vial for each blank value determination (i. Thus. The first sample of the next loop is then transferred into the oven and the water determination begins. > 15 μg H2O/min). For each series. the last sample vial that was baked out remains in the oven until the temperature has stabilized at the temperature of the next loop and the drift is low and stable. and thus the moisture adsorbed on the glass walls is not always the same. If the temperatures of successive loops are different. the moisture content is somewhat lower. In the same way. With rapidly changing.the analysis times for the determination of the blank value and for each sample are the same. suboptimum conditions. In this case. a blank determination can be performed between two sample loops. Important: After a blank value determination. etc. you can check whether the drift is constant and the new drift value can be used for the next series. as well as the anolyte in a coulometric analysis.e.

see also list of results). A special (longer) gas inlet glass tube is provided to bubble gas into the liquid. Use the same vials for a sample series as well as for the blank value determination. This is necessary so that the KF solvent or anolyte is not aspirated into the hot sample vial if Stromboli is not properly shut down while it is still hot. that the inert gas stream to the gas source is closed and the system is ventilated with ambient air. evaporated solvent is not condensing in the drying tube. you can not only determine solids but also liquid samples. Set a gas flow of 40–60 mL/min.g. The amount of moisture adhering to the glass surface of the sample vials strongly depends on how the vials were treated beforehand (cleaning. To check the titrator/drying oven system. These are partially vaporized (e. A sudden shutdown of power immediately switches the valve in that way. This test also serves to check the tightness of the oven and the connection tubing 65 . 7. toluene.g.55% or VWR/VWR/MERCK water standard KF oven 1%. 2. Vials that have undergone different treatment can show differences in the blank value of 50-150 μg water. since it provides a leak free inert gas stream during normal operation. In this way. 4. Therefore no precious inert gas is lost and no vacuum is applied to the system which may result in a back aspiration of the anolyte into the hot oven. 6. motor oil) or completely vaporized (e. you can use SIGMA-ALDRICH HYDRANAL® water standard KF oven 5. Allow sample vials that have been used or cleaned to stand overnight in the atmosphere for conditioning before starting measurements. 8.METTLER TOLEDO Good Titration PracticeTM in KF Titration Comments on the operation with the STROMBOLI oven sample changer: 1. With STROMBOLI. The delivery tube has a T-piece that causes a small leak flow. This has a large effect on the blank value and thus on the result. bent drying tube. An optional 3/2 way valve which is automatically controlled by STROMBOLI can be used instead of the T-piece mentioned in 1. and therefore it does not drop into the cathode compartment. 5. KF Coulometer C30: The internal drying tube of the generator electrode has to be replaced with an external. drying and storage). 3. This valve shall be used especially if inert gas sources are used.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

Examples:
Sample Result [ppm] No. of samples srel [%] T [°C]
Max.Time

[s]

Comments

Polylactic acid 0.5 g Polymer ABS-50 T 10014 3g Polymer ABS-50 F10014 2g Motor oil 1120/03 (AA) 2g

2589

3

1.1

160, air 190, N2gas 170, N2gas 165, air

--

Stir time: Max. time: rel. drift:

600 s 300 s 3 µg/min

736

5

1.1

300

Stir time: 900 s Delay time: 300 s Stir time: 900 s Delay time: 300 s Stir time: 60 s Delay time: 300 s Very slow evaporation, not faster with 180°C, above 180°C decomposition Stir time: 60 s Delay time: 300 s Very slow evaporation, above 180°C decomposition

1312

13

0.9

300

241 261

3 4

4.4 7.9

1500

Motor oil 1034/03 (AA) 1.5 g

426 438

4 3

2.7 4.5

180, air

1800

66

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

8 Measurement results
8.1 Resolution and detection limit
The following table indicates the theoretically smallest increments of current (KF coulometric) and titrant (Volumetric KF) which could be achieved by the instruments based on their technical specifications. Therefore, these are indicative values and they should be considered as such:
C20/C30 Compact Coulometric Instrument V20/V30 Compact Volumetric Titrator Resolution: 20’000 burette steps
5 mL burette: 0.25 µL c=5 mg H2O/mL: 1.25 µg H2O/step

Theoretical smallest increment

0.1 mC
Theoretical: Resolution:

(100 mA x 1 ms)
0.01 µg H2O < 0.1 µg H2O

Detection limit (limit of detection, LOD)

10 µg
Example: 10 g sample → determ. of 1 ppm Assumptions: - Current is used for iodine generation - Generated iodine is reacting 100% with water only.

50 x resolution
5 mL burette: 12.5 µL c=5 mg H2O/mL: 62.5 µg H2O Example: 5 g sample → determ. of 12.5 ppm

The theoretically smallest current increment that can be generated by the C20/C30 Compact Coulometers is 0.10712 mC which corresponds to 0.01 μg water. However, the achievable resolution of the instrument is in the order of less than 0.1 µg H2O, whereas the detection limit (also called “limit of detection”) is approx. 10 μg water per sample. Thus with a 10 g sample, 1 ppm water can be determined. For the V20/V30 Compact Volumetric instruments, the detection limit mainly depends on • • • The resolution of the burette drive, i.e. the max. number of steps which can be achieved by the stepper motor. the burette volume size; generally, a 5 mL burette is used for volumetric KF titration. The concentration of the titrant.

8.2 Measurement accuracy
The accuracy strongly depends not only on the technical specifications of the instruments, but also on the several factors that have been already mentioned in the previous chapters: 1. Sampling (including suitable storage, if necessary) 2. Sample treatment and preparation 3. Expected water content and selection of suitable instrument 4. Selection of optimum sample size 5. Condition of the KF reagents, i.e. fresh reagents, pre-titration, low drift value, … 6. Sealed titration vessel and tight tubing, 7. Condition of the indication electrode 8. Coulometry: condition of the generating cell 9. Parameter settings in the titration method etc. 67

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

To determine the closeness of agreement between the result of measurement and the true sample value, measurements can be performed either by titrating water standards or by titrating samples with known water content. The measurement accuracy depends on all the various factors described and explained in the previous sections. The crucial factors are optimum control as well as the water content and the amount of the sample.

8.3 Repeatability
The closeness of the agreement between the results of successive measurements of the same sample can be expressed quantitatively as the relative standard deviation, srel, given as %. With optimum sample amount and control, the following values can be obtained under test conditions for repeatability. The graph shows the relative standard deviation for different water contents. In general, the repeatability of a sample series becomes worse with decreasing water content. Note that for water content below 10 ppm it is not recommended to use a volumetric technique.

100% 10% 1% 1000 ppm 100 ppm 10 ppm 1 ppm

Coulometry
Not suitable for coulometry

Volumetry
srel < 0.5 %

srel < 0.5 %

srel 5 - 0.5 % srel 5 - 0.5 % srel > 5 % srel > 5 %
Not suitable for volumetry

In the following graphs, the relative standard deviation srel (%) of several series with different water content are given as a function of the sample size:

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0 5.0 3. it is necessary to use the optimum sample size in order to achieve precise results.METTLER TOLEDO Good Titration PracticeTM in KF Titration Relative standard deviation srel vs. sample size for different water contents: KF Coulometry KF Volumetric Titration: srel (%) 6 110 ppm 5 330 ppm 4 720 ppm 3 2 1 0 0. Therefore. A good repeatability is achieved the sample size is increased particularly for low water content values.0 2.5 1. 69 .25 0. with decreasing sample size the relative standard deviation srel becomes worse.0 Sample size (g) In both cases.

METTLER TOLEDO

Good Titration PracticeTM in KF Titration

9 Interferences
9.1 Effects of temperature
Temperature effects on the KF titrant The Karl Fischer titrants consist of approximately 90% methanol or ethanol. Their volume increases considerably if the temperature increases, and their concentration decreases accordingly. S. Eberius [3] specifies a correction factor of 0.0012 per degree Celsius for methanolic Karl Fischer solutions. According to ISO 760, a temperature increase of 1 °C causes a drop of 0.1% in the concentration. The titrant (in particular, the two-component KF solvent) may loose sulfur dioxide if the temperature rises. This causes bubbles to form in the titrant tubing, an effect which is worse the faster the rate at which the burette is filled. These titrators allow you to define the filling rate of the burette separately for each titrant, e.g.:
Temperature / °C < 15 15 – 30 > 30

Filling rate for one-component KF volumetric titrant / % Filling rate for two-component KF volumetric titrant / %

100 80

100 60

70 40

Titration at low temperatures You can perform Karl Fischer titrations at low temperature to eliminate undesired side reactions. The water content of peroxides, for example, can be determined at -40 °C. You must use the two-component reagent to do so, because the reaction rate of the onecomponent reagent is too slow at this temperature. Titration at high temperatures Increasing the titration temperature speeds up the dissolution of the sample or the extraction of the water from it, resulting in shorter titration times. Titrations at elevated temperature have proved particularly effective for foodstuffs, e.g. sugar, flour, potato flakes, hazelnuts, custard powder. The maximum temperature depends on the boiling point of the reagent (boiling point of methanol: 64 °C, boiling point of ethanol: 78 °C).

9.2 Side reactions
Side reactions that falsify the results can occur parallel to the Karl Fischer titration. There are mainly three side reactions that can affect the result: 1. Reaction with methanol, CH3OH Aldehydes and ketones react with methanol leading to additional water Esterification with carboxylic acids leading to additional water Ketones and aldehydes react with sulphur dioxide, a base and water (i.e. water is consumed) The reaction of iodine with e.g. oxides, hydroxides, carbonates, amines, ascorbic acid, and mercaptans leads to a higher consumption of iodine giving higher water content.

2. Reaction with water, H2O

3. Reaction with iodine, I2 -

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Good Titration PracticeTM in KF Titration

9.2.1 Reaction with methanol
Aldehydes and ketones: Methanol, CH3OH, reacts with aldehydes (R-CHO) and ketones (R-CO-R) to form acetals (CH3-CH(OR2)2 , and (CH3)2C(OR2)2 respectively, the latter also called ketals), as well as water: Formation of acetals:

CH3CHO + 2 CH3OH
Formation of ketals:

→ →

CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O

(CH3)2CO + 2 CH3OH
Solution: -

Use the special reagents for aldehydes and ketones with these substances (so-called K-reagents). They contain other alcohols than methanol. - Experiments have shown that the side reaction still takes place despite these reagents. Each time acetone is determined, for example, the drift is higher than before the titration: the larger the sample, the greater the drift increase. It is therefore recommend to perform the determination with a small sample amount and to replace the solvent after two or three samples. Esterification: Methanol, CH3OH, reacts under presence of strong acids (i.e. sulfuric acid) with carboxylic acids (R-COOH) to an ester (R-O-CO-CH3) and additional water:

R-COOH + CH3OH →
Solution: -

R-COO-CH3 + H2O

First neutralize the sample using a suitable base (imidazole) before KF titration.

9.2.2 Reaction with water
Another side reaction, the bisulfite addition, occurs with aldehydes and ketones in the presence of SO2. Water is consumed in the process. Bisulfite addition:

CH3CHO + H2O + SO2 + NR R1-CO-R2 + HSO3Note: SO2 + H2O = HSO3- + H+ Solution:

→ →

HC(OH)SO3HNR R1(R2)C(OH)SO3-

- Start the titration immediately after adding the sample. - Perform a fast titration by predispensing 90% of titrant consumption This causes the water to be titrated quickly, before any bisulfite addition can take place. The "Autostart" parameter allows for the automatic start of the titration as soon as the sample has been added and water is detected.

9.3 Reaction with iodine
The Karl Fischer reaction is a REDOX reaction with iodine as the oxidizing agent. Thus, iodine may also react with readily oxidizable samples. On the other hand, iodine can also be reduced by SO2 in some samples such as e.g. oxides. Both reactions cause additional iodine being consumed, giving a false higher water content.

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Good Titration PracticeTM in KF Titration

The following substances can react with iodine:
Ascorbic acid Boric acid, H3BO3 Disulfite, S2O5 2– Hydroxide, OH– Mercaptans, R-SH Peroxide, R-O-O-R Sulfite, SO3 Tin(II) salts
2–

Arsenite, AsO2 – Tetraborate, B4O7 2– Iron(III) salts Hydrogencarbonate, HCO3– Nitrite, NO2
– 2– 2–

Arsenate, AsO4 3– Carbonate, CO3 2– Hydrazine, N2H4, and its derivatives Copper(I) salts Oxides, e.g. CaO, MgO, MnO2 Silanols, R3-Si-OH Thiosulfate, S2O3 2–

Selenite, SeO3 Tellurite, TeO3

Solution: The Karl Fischer titration for the majority of these substances can be performed with the aid of the drying oven, or also by performing an external extraction.

9.4 Example: reevaluation of side reactions
The water content obtained is too high if side reactions previously described have occurred. This can also be the case if a drying oven is used, and the sample slowly decomposes. Nevertheless, the correct result can be reevaluated by graphical extrapolation. Example: Water determination in red polypropylene fibers.
µg water

250 °C 160 °C 120 °C

300 200
115 mg 640 ppm

100

0

5

10

15

20 min

The determination was carried out for a period of 20 minutes (max. time) with the drying oven set to 120 °C, 160 °C and 250 °C. The following results were obtained:

120 °C 1186 ppm

160°C 1442 ppm

280°C 1955 ppm

The volume-time curve clearly indicates the occurrence of a side reaction, which becomes faster with increasing the temperature. The "water content" increases with temperature. By reevaluation using the LabX® titration PC software the actual water content can be obtained by extrapolating the titration curve to time t = 0 min (green dotted lines). The content is 115 mg water; this corresponds to a water content of 640 ppm for a sample weight of 0.18 g. The extrapolated result was confirmed by an external extraction in methanol. In fact, the result obtained with this method was 610 ppm.

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titration never ends Very long pretitration Poor repeatability Wet anolyte .Use t(max) as termination parameter . .Replace anolyte Amount of sample too small .Clean the platinum pins of the measurement electrode with paper tissue .Check whether titration stand is completely tight. .Add a small amount of one-component KF titrant to the catholyte.Measurement electrode is faulty Titration stand not protected against moisture .Higher oven temperature .Clean titration cell and generator electrode and dry at 50 – 80 °C .The repeatability is strongly dependent on suitable sample preparation and sample addition.Increase amount of sample to ensure that approx.Increase end point Oven: water vaporizes very slowly and irregularly .1 Coulometry Problem Possible causes and action to take Anolyte is not bright yellow but dark yellow to brown Drift is too high after the pretitration of a fresh anolyte .Check whether titration stand is completely tight. Oven: .Use smaller sample Long titration time. drift stop . e.Use a different method Oven: water not completely vaporized . .Use higher oven temperature .Replace silica gel and molecular sieve in the gas drying unit The drift remains too high during standby titration Drift is too high after the titration of a sample Side reaction with the anolyte .Replace anolyte .Increase vaporization time.Use rel.Replace molecular sieves and silica gel in drying tube . drift stop as termination parameter. Water distribution in the sample is not homogeneous .g.Measurement electrode is not plugged in .Grease the tapered joints Moisture from cathode compartment and diaphragm . increase t(max) Wrong control parameters . especially at low water content (< 1000 ppm) 73 .Lengthen vaporization time (increase t max) .Increase value for rel.METTLER TOLEDO Good Titration PracticeTM in KF Titration 10 Troubleshooting 10. 1 mg water per sample is present.Homogenize sample.Level of anolyte should be higher than that of the catholyte . if possible increase amount of sample Wrong sample preparation and sample addition .

If the sample preparation and addition is not done carefully. Checking drying oven Out of limits.Add sample into KF reagents. bad repeatability Platinum parts of the generator are colored black Warning: “Conductivity too low” 74 .Use higher oven temperature . drift stop . For samples with very low water content < 30 ppm . the Coulometer must be adjusted With water Standard KF Oven 1 %.use a bigger sample size up to 0. at 170 °C.Sample is oxidized: use nitrogen as a purge gas Checking coulometer Out of limits.Use fix generator current 100 mA .Extend tmin (minimum titration time) Incomplete sample addition .Clean titration cell and measurement electrode Poor sample preparation and addition Samples of low water content (< 1000 ppm) are always hygroscopic. if it is defective. bad repeatability With water standard 1.Add chloroform or another solvent (maximum of 30%) to the anolyte to dissolve the sample Oven: .Lengthen vaporization time (increase t max) .Replace or repaire generator electrode.Sample not thermal stable: Use lower oven temperature . Sample not dissolved (emulsion) .Check drift and blank value . do not splash to the walls of the cell. .0.METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon . contamination with atmospheric moisture occurs.Too high value: see above “too high value” .Reduce the value for rel.Replace anolyte If this doesn’t help. It has no influence to the result.Use start cautious Oven: .Replace anolyte . Anolyte has too low conductifity .3 g Generator electrode is contaminated The black cover cannot be removed.0 or 0.Replace or change the anolyte .Too low value: see above “too low value” if this does not help. .1 mg/g . 10 – 15 minutes .Use back weighing. check generator electrode.2 .Use smaller sample size Values too high The titration was too fast → overtitration .

.Increase vaporization time.Increase oven temperature . e. drift stop" as a termination parameter.Replace molecular sieves and silica gel in drying tube . e. Titration stand not protected against moisture . drying oven. Wrong control parameters . Side reaction of the sample with the KF reagent .Check and optimize control parameters.Use longer mixing time or different solvents which dissolves the sample or extracts the water quicker.see above Oven: .The repeatability is strongly dependent on suitable sample preparation and sample addition.Extend vaporization time (increase t max) .Use "Rel. . Water distribution in the sample not homogeneous .Increase amount of sample to ensure 10 mg water per sample.Use different method. increase t(max) Long titration time.Clean platinum pins of the electrode with a paper towel. if possible increase amount of sample. Low water content (<1000 ppm)! .Grease the tapered joints Condition Titration stand . external extraction. titration never ends Wrong termination parameters .Increase endpoint potential Oven: water vaporizes very slowly and irregularly .g.Use higher oven temperature .Reduce sample size Poor repeatability of the results Amount of sample too small .Replace silica gel and molecular sieve in the gas drying unit Drift too high after titration of a sample The sample has not completely dissolved and continuously releases water .Use t(max) as termination parameter . etc. 75 .Increase value for relative drift stop.2 Volumetric Karl Fischer Titration Problem Possible causes and action to take Titrated solution is dark Drift too high after pretitration of fresh solvent Overtitration . Oven: water is not completely vaporized . .METTLER TOLEDO Good Titration PracticeTM in KF Titration 10.Shake titration vessel The drift remains too high during standby titration Titration stand not protected against moisture .Check whether titration stand is completely tight.Homogenize sample.Extend tmax (maximum titration time) .g.

METTLER TOLEDO Good Titration PracticeTM in KF Titration Problem Possible causes and action to take Values too low The titration was terminated too soon .Extend vaporization time (increase t max) .12 g in 40 mL.Sample is not thermally stable: Use lower oven temperature . Water as standard requires practice The use of water for the concentration determination requires experience to obtain repeatable and accurate results. No more sulfur dioxide in the solvent . which dissolves the sample. Di-sodium tartrate has only limited solubility In methanol max.55 % at 220 °C.Samples of low water content (<1000 ppm) are always hygroscopic. Poor sample preparation and addition . 0.Add chloroform or other solvent to methanol.Check drift and blank value .Replace the solvent frequently.Use titrant with 2 or 1 mg/mL Oven: .Change solvent or use fresh solvent after every sample. The concentration determination is correct only if the di-sodium tartrate has completely dissolved.Replace solvent . Sample not dissolved .Reduce the value for rel. If the sample preparation and addition is done carefully. bad repeatability 76 .Extend tmin (minimum titration time) Incomplete sample addition . drift stop . Oven: .Increase sample size up to 0. Determination of the concentration using di-sodium tartrate or Water Standard 10. For samples with low water content < 400 ppm . 15 – 20 minutes .Use higher oven temperature . contamination with atmospheric moisture occurs.4 g Increasing value in the concentration determination with di-sodium tartrate Checking drying oven Out of limits.Reduce dVmax and dVmax factor. With water Standard KF Oven 5. .0 is a simpler and a more dependable method.Sample is oxidized: use nitrogen as a purge gas The results in a series are continuously decreasing Very slow titration with twocomponent titrant Wrong or greatly fluctuating values in the concentration determination with water Dissolving capacity of the solvent is exhausted .Change solvent.Reduce sample size Single values too high Control parameters too fast (= slight overtitration) .Use back weighing.

nitrobenzaldehyde > C12 Stearyl alcohol. C0 V2.V4. salicylic acid High pKa value: 2-chlorophenol.V5 C20. C20 V11 C0 V2. bitumen V4.V5 C20 Ethers Linear and cyclic V2. e.: benzamide. indole.V4. o-cresol Side reaction: naphthol.V4. V3. V4 C20 Mercaptans V0.C22 V16 C0 V10 C0 Nitrocompounds V3. V3.1.g. V3.1 Solid samples 11. diphenylmethanol Weakly basic pKa >8: Imidazole.V3. nitrochlorobenzene Dialkylperoxide R-OO-R Alkylperoxide R-OOH Diacyl peroxide V0.V3.V3 C20 di-Nitrobenzene. stearamide Weakly acidic: benzoic acid Strongly acidic: malonic acid. V4 V2.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11 Karl Fischer Titration: The Method at a Glance 11.C22 V2. oxalic acid Oxidizable with iodine: ascorbic acid V2.V7 V2. V4 C20 V2 C20 Substance Halogenated hydrocarbons Isocyanates Ketones Examples R-Cl. R-Br.1 Organic Chemicals Substance Acetals Aldehydes Mono-/polyalcohols Amines Examples R1-CH-(OR2)2 Chlorobenzaldehyde. C0 Esters Carboxylic acid ester R-COOR´ Carbonic anhydride ROCOOR´ 77 . R-I R-NCO Benzophenone Method V2. C0 Sulfur compounds Phenols V0.V4 C20 Carbamates Carboxylic acid amides Mono-/polycarboxylic acids RO-CONH2 R-CONR´. cresol.V8 C20 V10. aminophenol Aromatic/aliphatic sulfonic acids sulfides R-S-R´ disulfides R-SS-R´ thiocyanates R-SCN V0.V3.pyren e. naphthalene > C20 Tar. toluidine Oxidizable with iodine: aminophenol Method V2. C0 Peroxides V2. anisidine. carbazole Strongly basic: aminopyridine Reaction with methanol: naphthylamine. V4 C20 V2. V4 C20 V15 C20 V0. nitrotoluene.V5 C20.V4. anthracene. C24 Hydrocarbons > C12 Biphenyl. C0 V2 C20 V15 Low pKa value: phenol. V5 C20 V2.

C34 V10 Na2HAsO3 . oxides Halogenides Examples Method V30 C30 V34 C32 V31 C32 V21. Na2HPO4 tert.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. NaHCO3 Na2CO3 B2O3 . C32 V31 C32 Thiosulfates Tin(II)salts Na2S2O3. Insoluble: pigments. poly-amides. lotion Lipstick Soaps Toothpaste V4.1.2 Inorganic chemicals Substance Arsenic compounds Bicarbonates carbonates Boron compounds Hydroxides. indicator dyes. creams Suppositories Tablets Lyophilized preparations V2 V4.3 Technical products – organic Substance Agrochemicals Dyes Examples Method V2 Substance Petrochemicals Examples Method V12 C0 V7 V5. V31 C32 V2. V32 C21. V31 C31. V32 C21. 78 . KJ. ZnSO4 V2. ski wax Tar. V8 Cosmetics Creams. V5 V12 V2 V40. etc. CaO NaCl. polypropylene.g. MgCl2 Cu(I) salts: CuCl2 NaH2PO4 . C34 V2. C32 V15. polystyrene. bitumen lubricating grease. dispersion dyes Waxes. glue stick Rubber cement Textile auxiliaries Surfactants powder optical brightener Plastics Polymers Polyethylene. NH4NO3 Nitrites NaNO2 11. disinfectants Salves. Phosphate. paraffins: shoepolish. CaCl2 . polyurethane. V31 C20. C34 V2. herbicides Soluble: wool dyes. V32 C20. V30 Insecticides. C34 V31 C33 V2. e. V32 C20.C40 V2 Adhesives All-purpose glue. C32 V31 C32 Sulfates Silicon compounds Substance Phosphates Examples Method V2. NaSO3 Na2S2O5 SnCl2 Nitrates NaNO3 . etc. H3BO3 NaOH. Silicon dioxide Silanols R3Si(OH) Na2SO4. C32 Pharmaceuticals Antibiotics. V31 C20. KOH MgO. V5 V5 V2 V20 V2 V5 V30.1. PVC. HBO3 .: Na3PO4 Silicon oxide. fungicides. V31 C20. multipurpose grease V2 V2. NaAsO2 KHCO3 .

1. sea salt V23 V24. V5 V5 Sugar and sugar products V13 V13 Sugar: total water cont. (V30) Cheese. mixed spice Mustard Adherent moisture: plain salt. instant coffee. ice cream Dried albumen Powdered milk V2 V13 V2. potato chips Potato flakes Dough. candy. coffee beans. silk 11. wheat. (V25) V22. C30 V2 V20 Paper. corn. Zwieback. caramel. plaster.inorganic Substance Building materials Fertilizers Examples Method V32 (C34) V6 Substance Minerals Detergents Examples Method V32 V30.. pudding powder.1. mayonnaise Shortening. gummi bears. margerine. V23 Vegetable products V22.almonds instant coffee Fats Butter. curry. wood Cellulose powder Wool. Zwieback Yogurt. tobacco. perborates) without brightener Total water V30 V2 11. dried vegetables and fruits Hazelnuts. (V5) V6 C23 V32 C34 V8 V2 V6 V5 79 . jellied fruits. noodles.5 Technical natural products Substance Cellulose products Fibrous materials Examples Method V30. noodles. meat spread. sea salt Total water: plain salt.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. jelly Sugar: adherent moisture Chocolate Spices Pepper. V23 V30. tea. cement Adherent moisture Zeolites Laundry detergent with brightener (hydroxides. hardened fat V4.6 Food Substance Protein products Examples Method V23 Substance Grains and starchy foods Examples Method V13. rye. V21 Mortar. almond paste Instant ice tea. V23 Cacao. broth Biscuits. jam Honey.1.4 Technical products .

nitrotoluene. nitrochlorobenzene Acetonitrile V16 C0 Nitrocompounds V1 C1 V10 C0 Nitriles V1 C1 V0 C0 Peroxides H2O2 V15 Carboxylic acids C1 to C2 formic acid. methylal C1 to C7 hexane. diamine Easily oxidized with iodine: hydrazine. acrylic acid V15 C0 V1 C1 V1 C1 V1 C1 V1 C1 Acid amides Dimethylformamide Sulfides. benzyl alcohol Weakly basic: N-methyl aniline heterocyclic amines pyridine. hexanol. ethyl acetate Methyl chloride.2. chlorobenzene. ethylal. disulfides sulfonic acids Mercaptans V1. xylene C7 to C14 gasoline. petroleum. hydroxylamine V1 C1 V1 C1 Mineral acids V5 C30 V15 C0 Amines H2SO4. benzaldehyde V11 C0 saturated and unsaturated V4 C1 Alcohols Propanol. cyclohexene. hexylamine Reaction with methanol: aniline. benzene. HCl Nitrobenzene. isobutane. toluene. dodecane > C14 heavy oil.1 Organic and inorganic chemicals Substance Acetals Examples Method V1 C1 Substance Hydrocarbons Examples Method V1 C1 Acetal. crude oil. paraffin Aldehyde Acetaldehyde. C1 Sulfurcompounds V1 C1 V0. anisole Methyl benzoate.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. chinoline Strongly basic: alihatic amines N-butylamine. HNO3. acetic acid > C2 propionic acid. chlorotoluene Acetone. pentane. cyclohexane. dioxane. acetophenone.2 Liquid samples 11. C0 Ethers Esters Halogenated hydrocarbons Dimethylether. toluidine. methylethylketone Ketones V10 C10 80 . t-butyl chloride.

massage oil Vegetable oils Technical oils Hydraulic oil. condensed milk Tensides and detergents Agrochemicals (sprays): herbicides. 81 . transformer oil. sample input and titration methods. fungicides Acrylic enamels Emulsions in solvents V1 V1 V29 V4 C1 V7 V4 C1 V4 C1 Agrochemicals (sprays): insecticides Synthetic enamels Foods: salad oil.3. tinctures Cosmetics: perfume. shampoo Method V1 V1 V1 V1 V4 Tensides and detergents Aqueous emulsions Milk products: milk.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. silicon oil Motor oils V5 C1 V30 C30 For more details on the sample preparation. cream.2. liquor Pharmaceuticals: extrakts. wine. refer to chapter 11. brake fluid.2 Foods and technical products Substance Aqueous solutions Examples Foods: spiced sauce: soy sauce beverages: beer. sunflower oil Pharmaceuticals and cosmetics: ethereal oils.

10 minutes V4 V5 V6 V7 V8 V10 V11 V12 82 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: KF solvent / chloroform 1:1 to 1:2 Stir time: 60 .1 Volumetric methods The methods have been developed using 2-component reagents.120 s Delay time: 7 seconds.120 s V2 V3 Direct titration with added 2-propanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / propanol 1:1 Stir time: 60 .120 s Direct titration with added chloroform Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / chloroform 1:5 Stir time: 60 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.120 s Direct titration with added formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 5 .10 minutes Direct titration methanol free Titrant: two comp.3 Titration Methods 11. In this case methanol is used as a solvent. dProcedure V1 Direct titration Titrant: Solvent: Stir time: Direct titration Titrant: Solvent: Stir time: two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 10 s two component reagent 5 or 2 mg H2O/mL 40 mL KF solvent 60 . reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Stir time: 30 – 60 s Direct titration methanol free Titrant: two comp.120 s Direct titration with added 1-decanol Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / 1-decanol 1:1 Stir time: 60 . reagent 5 mg H2O/mL for ketone und aldehyde Solvent: 40 mL KF solvent for ketone und aldehyde Start immediately (autostart) Direct titration with heat (at 50°C) Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent Stir time: 5 . Direct titration with added toluene Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 40 mL KF solvent / toluene 1:1 Stir time: 60 .3. These can be also performed using the one-component reagent.

Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with methanol at 50 °C Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide 1:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with 1-decanol/formamide/methanol 8:2:1 Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent External extraction with formamide Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 With drying oven at 110 .150°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .220°C Titrant: two component reagent 5 or 2mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .20 min Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated solvent and inject entire solution into titration cell and titrate.METTLER TOLEDO Good Titration PracticeTM in KF Titration V13 Direct titration with added formamide and heat.20 min With drying oven at 300°C Titrant: two component reagent 5 or 2 mg H2O/mL Solvent: 50 mL KF solvent Stir time: 10 .20 min With drying oven at 160 .15 minutes Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 20 mL buffer or 7g imidazole Stir time: 60 .120 s Direct titration with neutralization Titrant: two component reagent 5 mg H2O/mL Solvent: 30 mL KF solvent and 5 g benzoic acid Stir time: 1-2 minutes External extraction with methanol at room temperature Titrant: two component reagent 5 mgH2O/mL Solvent: 30 mL KF solvent External extraction with methanol at room temperature in sonicator Remove aliquots of extraction solution over membrane filter with syringe. 50°C Titrant: two component reagent 5 mg H2O/mL Solvent: 40 mL KF solvent / formamide 1:1 Stir time: 10 . Titrant: two component reagent 2 mg H2O/mL Solvent: 50 mL KF solvent Side reaction: KF titration not possible V15 V16 V20 V21 V22 V23 V24 V25 V29 V30 V31 V32 V40 V0 83 .

METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with 1-decanol or external dissolution in 1-decanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with chloroform or external dissolution in chloroform Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction or external dissolution in chloroform (methanol free) Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones With drying oven at 110-130°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 140-150°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 160-190°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 200-250°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes With drying oven at 300°C Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Titration time: 10-20 minutes Special method for lyophilized preparations Dissolve sample in septum flask with 10-20 mL titrated anolyte and inject entire solution into titration cell and titrate. Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent Coulometric determination not possible C10 C20 C21 C22 C23 C24 C30 C31 C32 C33 C34 C40 C0 84 .3.2 Coulometric methods Method C1 Procedure Direct titration Anolyte: Catholyte: 100 mL anode reagent 5 mL cathode reagent C5 Direct titration with added chloroform Anolyte: 70 mL anode reagent and 30 mL chloroform Catholyte: 5 mL cathode reagent Direct titration methanol free Anolyte: 100 mL anode reagent for ketones Catholyte: 5 mL cathode reagent for ketones External extraction with methanol or external dissolution in methanol Anolyte: 100 mL anode reagent Catholyte: 5 mL cathode reagent External extraction with Methanol in sonicator Remove aliquots of extraction solution over membrane filter with syringe.

S5 S10 S8 Paraffins. Press through small holes e. pastes Pulverized soluble Salves. Stir. paper. Let solids settle and remove aliquot of remaining solution with syringe. ice cream.g. noodles. S10 S2. shoepolish Creams. meat grinder.METTLER TOLEDO Good Titration PracticeTM in KF Titration 11.4. jelly. After sample removal keep sample sealed. (Select stir time so that sample dissolves completely. wool. (Pre-heat syringe with hair dryer or in drying oven. 1-decanol. broth Hardened fat. chocolate Method S1 S1. SiO2 Salts.2 Solids: Sample input Method S1 S2 S3 S4 S5 S6 S7 Sample input finely ground sample with weighing boat finely ground sample with weighing boat finely ground sample with weighing boat with spatula with spatula or weighing boat with spatula or weighing boat with spatula Do not use syringe. cooled analysis mill. rocks e. Use grate to reduce size. In external extraction solvent (methanol. Homogenize sample well. or up to approx. S3 S10. silk Cheese. pepper. After sample removal keep sample sealed.: CaCO3 .g. brittle Soft. S10 S11 S4. Pulverize with mixer. shake or sonicate. honey.8 mm S11 S12 syringe without needle (Fill very thick samples in back of syringe) weighing boat 85 .) Homogenize sample well.5 mm or without needle. 60° C. bitumen Method S7. resinous Waxes Examples Butter. margarine Phenols. potato flakes Tar. active ingredients Na-tartrate S9 S12 11. S11 S4.4 Sample preparation and input 11. tobacco.) S8 S9 S10 syringe with needle Ø 0. Dissolve sample or extract water. Break and disperse with high-speed mixer (up to 24000 cpm) in external extraction solvent (methanol. Inject into titration cell. Pulverize with mortar. cristalline products Wheat. creams gel. for very thick pastes drill hole in bottom of syringe. gummi bears. Melt sample. tea. formamide). Cut in small pieces with scissors or knife. No further preparation necessary. S3 S2. S2 S1. yogurt Salts. napthalene. coffee. At room temp. the moisture will be pressed out with pre-heated syringe (with needle Ø 0. S10 S11 S10. almonds. almond paste. brittle Hard natural products Fibrous natural products Tenacious products Soft products Hard. S8 S10 Property Soft. Use syringe with needle Ø 1.1 Solids: Characteristics Property Very hard Hard. greasy Examples Minerals. S11 S6.8 mm ) Fill in backend of syringe Procedure Grind in sealed. 1-decanol. Zwieback Dried vegetables and fruits. meat Jellied fruits.4. greasy Soft. formamide).

Remove sample immediately. toluene.4.Inject sample into titration cell through septum or needle hole of three-hole adapter with 10 mL syringe (with needle Ø 0. crude oil.Homogenize thoroughly by shaking or stirring prior to sample removal. acetic acid Silicon oil. . glycerine Hexane. after-shave Beverages. Hygroscopic sample or low moisture content (< 1000 ppm) . . .Keep sample in a septum flask. gasoline. aqueous emulsions Acrylic enamels.Rinse syringe with sample 2-3 times (pull up and discard) and condition for 5 minutes. 0°C in ice bath.8 mm) Injection with syringe (without or with needle Ø 1. .8 mm).8 mm ME-71482 ME-71484 Septum NS24 ME-23950 Three-hole adapter ME-23982 86 . . petroleum.Cool sample to approx. H2SO4. L2 L3 L4 L5 Injection with syringe L6 Injection with syringe after sample homogenization (with needle Ø 0.8 mm) to remove fresh sample from sample flask and inject this into titration cell through septum or needle hole of three-hole adapter. Turbid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. glycerine Acetaldehyde Methanol. Boiling point 5 .8 mm) Inhomogeneous emulsions .Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe. acetone.Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.8 mm) Injection with syringe Procedure Fluid liquid sample Inject sample into titration cell through septum or needle hole of three-hole adapter with 1 mL or 10 mL syringe.15°C Examples Propanol. salad oil Perfume.3 Liquids: Characteristics Property Liquid Turbid Low boiling point Hygroscopic Low moisture content Non-hygroscopic. cream Method L1 L2 L3 L4 L4 L1 L5 L6 11. 11.2 mm ME-71483 ME-23951 ME-51107668 10 mL 0. . acetone.5 Accessories for sample input Syringe Injection needle Weighing boat. detergents. synthetic enamels. glass Visco-Spoon™ 1 mL ME-71492 1.The pressure loss during sample removal must be compensated with dried air. average moisture content High moisture content Inhomogeneous (> 50%) (< 1000 ppm) 5 .METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. For each titration use 1 mL syringe (with needle Ø 0. milk.4.15 °C .4.5 mm) Injection with syringe after cooling sample (with needle Ø 0.4 Liquids: Sample input Method L1 Sample input Injection with syringe (with needle Ø 0. Samples with high moisture content (> 50%) Rinse syringe with sample 2-3 times.

.C. VERHOFF. BUNSEN. J. Chem. “Karl-Fischer Reagentien ohne Pyridin“. Z... Thesis University of Hannover. Chem. Th. J.. Anal. 256-260 (1989) (in German)...comparison with the aqueous system“.396 (1935). F. 265 (1853). 1999 (in German). MEYER. Z. C. 75-80 (1978). 94. Amer. „Karl-Fischer Reagentien ohne Pyridin. GRÜNKE. Chem. WERNIMONT. Anal. 203 . Soc. Fres.. Electroanal. VERHOFF. WÜNSCH. Anal. 71. “Analytical Procedures Employing Karl Fischer Reagent I. E. “Stöchiometrie und Kinetik der Karl-Fischer –Reaktion in Methanol als Reaktionsmedium”. Ind..W. 460-464 (1982). Part IV. Anal. J. „Kinetics and stoichiometry in the Karl Fischer solution“. Anal. 15 (4).M. 334. M. E. Electroanal. “Mechanism and reaction rate of the Karl Fischer titration reaction. See literature references in: EBERIUS. Electroanal. Eng. 30-32 (1981). 306. VERHOFF. BRYANT. W. 86. 312. 334. Chem. VERHOFF. A. . Fresenius Z. “Mechanism and reaction rate of the Karl Fischer titration reaction. S. Rotating ring disk electrode meassurement“. Fresenius Z. 309.. „Wasserbestimmung mit Karl-Fischer-Lösung“. Verlag Chemie Weinheim (1954) / (in German). P. HOPFKINSON. K. Chem. 139-147 (2000). Fresenius Z. 395-403 (1977). „The Dead-Stop End Point – As Applied to the Karl Fischer Method for Determining Moisture“. 86. Anal. BARENDRECHT. Chem. Einkomponenten Reagentien“. „Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes von Flüssigkeiten und festen Körpern“.. Nature of the Reagent”. BARENDRECHT.J.C. SEUBERT A.C. SMITH. „Mechanism and reaction rate of the Karl Fischer titration reaction. Part III. 305-315 (1976). Fresenius Z. Anal. „Karl-Fischer Reagentien ohne Pyridin. Analytical implications”. [3] [4] [5] [6] [7] 87 .C. J. Chem 368. Chem. MITCHELL jr. E. Diploma-Thesis at the University of Hannover / Germany. “Mechanism and reaction rate of the Karl Fischer titration reaction. SEUBERT A. SCHOLZ. 215 – 219 (1959). „Karl-Fischer Reagentien ohne Pyridin Genauigkeit der Wasserbestimmung“. J. 75. 31 (2). 48.... 407-415 (1978). VERHOFF.. Anal. J.. 394 .. „Karl-Fischer Reagentien ohne Pyridin. Chem.. 394 .. SCHOLZ. [10] GRÜNKE. E. J. PhD.. COFINO.396 (1981). Part V.. G. Chem. “Determination of Water by Titration with Coulometrically Generated Karl Fischer Reagents”. 272 – 274 (1943).6 References [1] [2] FISCHER. Rotating ring disk electrode meassurement . Anal. Chem. WÜNSCH... 1. Potentiometric measurements”.. R. Auflage. 2407 . Ed. “Untersuchungen zur Karl-Fischer-Reaktion”. Chem. G.207 (1980).METTLER TOLEDO Good Titration PracticeTM in KF Titration 11. Anal. E. E. Chem. E.. [8] SCHOLZ.S. G. 123-125 (1981). M. D. 705-717 (1976). W. E. 61. [9] WÜNSCH. SCHOLZ. “Mechanism and reaction rate of the Karl Fischer titration reaction. Acta.. SCHOLZ. Fres. 16-21 (1989) (in German).C. E. Fresenius J. Part II. J. Part I. J. Chem. Anal. Chim. 309. Electroanal. First and second order catalytic currents at a rotating disk electrode“. Neue Eichsubstanzen“. Chem. 303. 1988 (in German). KOK. J. J. Chem. Fresenius Z.2412 (1939). BARENDRECHT. A.4. W. Liebigs Ann. Chem. Both publications from: SEUBERT. G. 93... Angew. “Nebenreaktionen in Karl-Fischer-Reagenzien ”. Zweikomponenten Reagentien mit Imidazol“. BOYD. “Reaktionsmechanismen in der Karl-Fischer-Lösung“. S.

1984.Theorie und Praxis“. E. „Karl Fischer Titration“. Darmstadt / Germany. „Eugen Scholz Reagents for Karl FischerTitration“. GIT Verlag GmbH.A.. 431-435 (2006).. 11. D. "Coulometric Karl Fischer titration with a diaphragm-free cell: Cell design and applications". 2006.. Sigma-Aldrich Laborchemikalien GmbH..30918 Seelze / Germany.. 1985. 1989 (German) 88 . SCHÖFFSKI. „Wasserbestimmung durch Karl-Fischer-Titration . WIELAND.5 Additional literature HYDRANAL®-Manual. SCHOLZ. „Untersuchungen einer Karl-Fischer-Reaktion“. M. DE AGOSTINI A. DE CARO C. Food Chemistry 96. K.METTLER TOLEDO Good Titration PracticeTM in KF Titration [11] LANZ. RÜEGG K. G. Diploma-Thesis at the University of Hannover / Germany.. Springer Verlag Berlin..

89 . The sample P used for the extraction is not dissolved. WTOT : Water content of the supernatant extraction solvent (% or ppm) WL : mL : mP : Thus: 1) 2) 3) 4) 5) 6) 7) For % : C ⋅ [msol + (mext ⋅ R )] = R ⋅ mext + B ⋅ msol R C B msol mext Blank value (water content of the solvent. For ppm : R (ppm ) = 10 6 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 10 6 − C ⎝ mext since 1 = 106 ppm. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent C ⋅ msol + C ⋅ mext ⋅ R = R ⋅ mext + B ⋅ msol C ⋅ mext ⋅ R − R ⋅ mext = B ⋅ msol − C ⋅ msol R ⋅ (C ⋅ mext − mext ) = B ⋅ msol − C ⋅ msol R= 1 ⋅ (B ⋅ msol − C ⋅ msol ) (mext ⋅ (C − 1)) R= R= 1 ⋅ (C ⋅ msol − B ⋅ msol ) (mext ⋅ (1 − C )) since 1 1 =− 1− C C −1 1 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 1 − C ⎝ mext R (%) = 100 ⎛ msol B ⋅ msol ⎞ ⋅ ⎜C ⋅ − ⎟ mext ⎠ 100 − C ⎝ mext since 1 = 100%. Water amount after extraction = Water amount before extraction WTOT•(mL + (mP•WP) ) = WP•mP + WL•mL where Water content in the sample P (% or ppm). WP: This is what we get from the calculation in the KF method.1 Formula for the external extraction Principle: • • The water amount (in grams) after extraction is equal to the water amount before extraction.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12 Appendix 12. % or ppm).

ppm ) = C ⋅ ⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ 12.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. 90 .2 Formula for the external dissolution Principle: The water amount (in grams) determined by titration is the sum of the water amounts present in the solvent and in the sample. the total volume is increased.01% VWR/VWR/MERCK APURA water standard 0. Total water content (sample + solvent).00 mg/g (1000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. The sample P used for the external dissolution is completely dissolved into the solvent.3 Standards for Karl Fischer coulometry a) For direct measurements: VWR/VWR/MERCK APURA water standard 0. Thus. in % or ppm.55% (potassium citrate monohydrate) The water content is declared on a test certificate supplied with every vial. Blank value (water content in% or ppm) of the solvent.1 mg/g (100 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 1. Water amount after dissolution = Water amount before before dissolution WTOT•(mL + mP) = WP•mP + WL•mL where WP: WTOT : WL : mL : mP : Thus: 1) 2) 3) 4) C ⋅ [msol + mext ] = R ⋅ mext + B ⋅ msol Water content in the sample P (% or ppm) This is what we get from the calculation in the KF method. Amount of solvent (g) after determining the blank value Amount of sample (g) extracted with the solvent R C B msol mext C ⋅ msol + C ⋅ mext = R ⋅ mext + B ⋅ msol R ⋅ mext = C ⋅ msol + C ⋅ mext − B ⋅ msol ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R = C ⋅⎜ ⎟−⎜ ⎟ mext ⎝ ⎠ ⎝ mext ⎠ For % and ppm: ⎛ msol + mext ⎞ ⎛ B ⋅ msol ⎞ R(%.1% SIGMA-ALDRICH HYDRANAL®-Water Standard 0.

Alternatively. alcohols.4 Reagents and solvents for coulometric analysis To determine its total water content. esters.2 For samples that are poorely soluble in methanol or ethanol These include: etherial oils. nitrocompounds. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG-H (SIGMA-ALDRICH) contains approx. ethers. chlorinated hydrocarbons (up to C10). the sample must completely dissolve in the anolyte. acetamide. This means that if an emulsion is formed in the anolyte.4. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples.4. the anolyte must be immediately replaced. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat AG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Ethanol-based reagents: anolyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat E (SIGMA-ALDRICH) Methanol-based reagents: electrolyte:HYDRANAL® Coulomat AD (SIGMA-ALDRICH) - For cells without diaphragm: - APURA combiCoulomat fritless (VWR/VWR/MERCK) 12.e. ointments. etc. If the sample does not completely dissolve. more solvent can be added to the anolyte. edible oils.1 For samples that are soluble in methanol or ethanol These include: hydrocarbons (up to C10). etc. an emulsion is formed. In this case. 30% hexanol APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% hexanol catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit For cells without diaphragm: 91 . This is limited to a maximum of 30% to prevent the conductivity from falling too low. i. the water content determined is lower than the actual water content of the sample. A number of different anolytes are available to dissolve the various types of samples encountered in practice. 12. part of the water content is not measured.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12. hydrocarbons (C10 to C20).

the entire titration cell must be thoroughly cleaned because even traces of methanol may cause serious interferences. transformer oils. For cells with diaphragm: Methanol-free reagents: anolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) catholyte: HYDRANAL® Coulomat CG-K (SIGMA-ALDRICH) Methanol-free reagents: electrolyte: HYDRANAL® Coulomat AK (SIGMA-ALDRICH) When changing from normal KF anolytes to ketone reagents. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → (CH3)2CO + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O Special methanol-free reagents must be used for these substances. hydrocarbons (above C20). silicone oils. If you measure ketones regularly. etc.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal or an acetal and water.3 For samples that are insoluble in methanol or ethanol These include: petroleum oils. Chloroform must be added to the anolyte to ensure the solubility of these samples.4. For cells with diaphragm: Methanol-based reagents: anolyte: HYDRANAL® Coulomat A (SIGMA-ALDRICH) + 20% chloroform HYDRANAL® Coulomat AG (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat frit (VWR/VWR/MERCK) + 30% chloroform catholyte: HYDRANAL® Coulomat CG (SIGMA-ALDRICH) APURA combiCoulomat frit (VWR/VWR/MERCK) Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 30% chloroform APURA combiCoulomat fritless (VWR/VWR/MERCK) + 30% chloroform For cells without diaphragm: - 12.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based reagents: electrolyte: HYDRANAL® Coulomat AD (SIGMA-ALDRICH) + 20% hexanol APURA CombiCoulomat fritless (VWR/VWR/MERCK) + 20% hexanol 12. we recommend the use of a second titration cell. This is limited to a maximum of 30% in order to prevent the conductivity from becoming too low. For cells without diaphragm: - Notes on ketones: - - 92 .4.

5 to 7 (see Section 1.2). the substances can. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. The special reagent for ketones can also be used for other samples. After a longer standby period. it is possible that the anolyte is exhausted after a few days even though no further titrations have been performed. easily be measured with volumetric KF determination. the more important the effect of side reactions becomes.g. Fill the anode compartment with approx. e. benzaldehyde) can also be determined by coulometric KF titration. the pH value of the anolyte must be adjusted to the range 5. acetaldehyde) are oxidized at the anode with the formation of water. Coulometric KF titration cannot be used to determine these compounds. Aromatic aldehydes (e. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value).METTLER TOLEDO Good Titration PracticeTM in KF Titration - If you have titrated a number of ketone samples. Measure the pH with a glass electrode adjusted with aqueous buffers. 1 mL). - - Notes on aldehydes: - - 12.2 mL to 0. formic acid.g. with reactive ketones such as cyclohexanone use only 0.e. Short chain aldehydes (e.5 mL. e. acetic acid. i. 80 mL of anolyte and 20 mL HYDRANAL® buffer. Basic samples must be neutralized with salicylic acid or benzoic acid. etc.g. Choose relatively small samples (approx.4. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes.g. To do this. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. The larger the sample. however. In these cases the pH value of the anolyte should be measured. The use of imidazole increases the pH value in the anolyte. the drift is higher because of the very slow side reaction. Fill the anode compartment with approx. take an aliquot of anolyte from the titration cell. It is important to note that alcohols that react with ketones should not be titrated in this reagent.5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift. - For acidic samples.: - For basic samples. Use the HYDRANAL® buffer (SIGMA-ALDRICH). The measurement should not be performed in the titration cell because the electrode introduces too much water. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. amines: - 93 . With Karl Fischer titrations of acidic and basic samples.

more solvent can be added to the anolyte 12. an emulsion is formed. One-component reagents: 94 .0 mg/g (1000 ppm) SIGMA-ALDRICH HYDRANAL®-Water Standard 10. ethers.0 mg/g (10’000 ppm) b) For measurements with an oven: VWR/VWR/MERCK APURA Water standard oven 1% (tungstate) SIGMA-ALDRICH HYDRANAL®-Water Standard KF-Oven 5. i. If it does not completely dissolve. hydrocarbons (C10 to C20). nitrocompounds.5 Water Standards for Karl Fischer volumetric titration a) For direct measurements: VWR/VWR/VWR/MERCK APURA® water standard 0. acetamide. the anolyte must be immediately replaced. The water content is declared on a test certificate supplied with every vial.6 Titrants and solvents for volumetric analysis The sample must be completely dissolved in the anolyte to determine the total water content. edible oils.6. the result determined is lower than the actual water content. chlorinated hydrocarbons (to C10). etc.1% VWR/VWR/MERCK APURA® water standard 1% SIGMA-ALDRICH HYDRANAL®-Water Standard 1. alcohols. Octanol or hexanol can be added to the anolyte to improve the solubility of these samples.METTLER TOLEDO Good Titration PracticeTM in KF Titration 12.2 For samples poorly soluble in methanol or ethanol These include: etherial oils.6. In this case. ointments. esters. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: Dry methanol Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent Ethanol-based: Titrant: HYDRANAL® Titrant E Solvent: HYDRANAL® Solvent E (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: (SIGMA-ALDRICH) (VWR/Merck) - (SIGMA-ALDRICH) (SIGMA-ALDRICH) 12.e. This is limited to a maximum of 50%. In this case. etc. A number of different anolytes are available to dissolve the various types of samples encountered in practice. Alternatively.1 For samples soluble in methanol or ethanol These include: hydrocarbons (to C10). 12.55% (potassium citrate monohydrate). part of the water content is not measured.

MH apura® CombiSolvent Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) Two-component reagents: Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. with the formation of water. silicone oils. hydrocarbons (above C20).6. Chloroform must be added to the anolyte to ensure the solubility of these samples.3 For samples insoluble in methanol or ethanol These include: petroleum oils. Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12. etc.6. transformer oils. One-component reagents: Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® Solver (Crude) apura® CombiSolvent Fats Methanol-based: Titrant: HYDRANAL® Titrant apura® Titrant Solvent: HYDRANAL® Solvent CM. This is limited to a maximum of 50% in order to prevent the conductivity from becoming too low.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-based: Titrant: HYDRANAL® Composite apura® CombiTitrant Solvent: HYDRANAL® LipoSolver CM.4 For ketones and aldehydes Ketones and aldehydes react with methanol to form a ketal. Acetal formation: Ketal formation: CH3COH + 2 CH3OH → CH3CH(OCH3)2 + H2O (CH3)2C(OCH3)2 + H2O (CH3)2CO + 2 CH3OH → Special methanol-free reagents must be used for these substances. or an acetal. One-component reagents: 95 . Oil apura® Solvent Oil & Fats (SIGMA-ALDRICH) (VWR/Merck) (VWR/Merck) Two-component reagents: - (SIGMA-ALDRICH) (VWR/Merck) (SIGMA-ALDRICH) (VWR/Merck) 12.

The larger the sample. easily be measured with volumetric KF determination. amines: 96 . e.g. If you measure ketones regularly.2).5 For acids and bases (pH value) A noisy titration or a sluggish end point can indicate a pH shift.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Methanol-free: Titrant: Solvent: HYDRANAL® Composite 5 K apura® CombiTitrant 5 Keto (SIGMA-ALDRICH) (VWR/Merck) HYDRANAL® Medium K (SIGMA-ALDRICH) HYDRANAL® Working Medium K HYDRANAL® KetoSolver apura® CombiSolvent Keto (VWR/Merck) Notes on ketones: When changing to ketone reagents. The use of imidazole leads to a high pH value in the anolyte. With Karl Fischer titrations of acidic and basic samples. the substances can. It is important to note that alcohols that react with ketones should not be titrated in this reagent. however. Short chain aldehydes (e. To do this. e. etc. If you have titrated a number of ketone samples. 80 mL of anolyte and 20 mL HYDRANAL® buffer.6.2 mL to 0. i. This is why one should wait for the reverse cleavage reaction of the bisulfide compound before aborting the titration (ensure that the drift drops down again to the initial value). the pH value of the anolyte must be adjusted to the range 5. benzaldehyde) can also be determined by coulometric KF titration.g. - Notes on aldehydes: - - 12. Use the HYDRANAL® buffer (SIGMA-ALDRICH). take an aliquot of anolyte from the titration cell.g. formic acid. with reactive ketones such as cyclohexanone use only 0.: - For basic samples. Measurement with moistened indicator paper also gives an approximate indication of the pH value of the anolyte. Coulometric KF titration cannot be used to determine these compounds.g. acetaldehyde) are oxidized at the anode with the formation of water. Measure the pH with a glass electrode adjusted with aqueous buffers. the more important the effect of side reactions becomes.5 mL. the entire titration cell must be thoroughly cleaned because even traces of methanol can cause serious interference. Aromatic aldehydes (e.e. - For acidic samples. The special reagent for ketones can also be used for other samples. 1 mL). Choose relatively small samples (approx. It should be noted that the bisulfide-addition reaction is very strong with aromatic aldehydes. the drift is higher because of the very slow side reaction. The measurement should not be performed in the titration cell because the electrode introduces too much water. acetic acid. we recommend the use of a second titration cell. the drift increases from sample to sample so strongly that the determination of the endpoint becomes difficult. Fill the anode compartment with approx. In these cases the pH value of the anolyte should be measured.5 to 7 (see Section 1.

Keep away from open flames or sparks. Health hazard when inhaled.: 11 °C MAK value: 200 ppm Highly flammable. Ignition temp.: 28 °C MAK value: 100 ppm Flammable. Disposal: as an organic solvent. 2methoxyethanol or diethyleneglycolmonomethylether). buffer (imidazole) and solvent (methanol. 2methoxyethanol or diethyleneglycolmonomethylether).2 Two-component reagent: Composition: iodine and solvent (methanol. Disposal: as an organic solvent. 13 Hazards and waste disposal tips 13. Do not let reagent contact skin or eyes. The KF solvent contains: sulfur dioxide. Irritant when inhaled.3 Reagents for coulometry: Composition: iodine. buffer (imidazole). Skin irritant. Health hazard when inhaled.4 Safety data for the KF-components and auxiliary solvents: sulfur dioxide: iodine: diethyleneglycolmonomethylether: 2-methoxyethanol: MAK-value: 200 ppm MAK-value: 0. 2-methoxyethanol).: does not burn MAK vlaue: 200 ppm 97 methanol: o-xylene: chloroform: .: 46 °C MAK value: 5 ppm Flammable. Do not let reagent contact skin or eyes. Poisonous when inhaled or swallowed. swallowed or allowed to contact skin.1 One-component reagent Composition: sulfur dioxide. Potential teratogen. swallowed or allowed to contact skin. Keep away from open flames or sparks. Health hazard upon inhalation. 13. poisonous when inhaled or swallowed. Safety: flammable to extremely flammable. Irritant when inhaled.: 87 °C Ignition temp. 2-methoxyethanol. Disposal: as an organic solvent. Keep container tightly closed.1 ppm. Keep container tightly closed. Ignition temp. swallowed or allowed to contact skin. Health hazard when inhaled. Safety: Highly flammable. oxidant Ignition temp. sulfur dioxide. Keep container tightly closed and far removed from open flames or sparks.METTLER TOLEDO Good Titration PracticeTM in KF Titration - Basic samples must be neutralized with salicylic acid or benzoic acid. 90 mL of anolyte and 5 g salicylic acid or benzoic acid. Safety: flammable to extremely flammable. iodine. Fill the anode compartment with approx. Irritant when inhaled. Do not let reagent contact skin or eyes. 13. xylene or trichloroethaylene). tetrachloromethane. buffer (imidazole) and solvent (methanol. 13. Ignition temp. and solvent (methanol. chloroform.

Irreversible damage possible.: inflammable MAK value: 20 ppm Irritant for skin and eyes. Ignition temp. Ignition temp. Ignition temp. Health hazard upon inhalation 98 .: 95 °C Irritant for skin and eyes.: 6°C MAK value: 20 ppm Extremely flammable. Potential teratogen.METTLER TOLEDO Good Titration PracticeTM in KF Titration 1-decanol: formamide: toluene: Health hazard when inhaled.

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Analytical Sonnenbergstrasse 74 CH-8606 Schwerzenbach. www. are two powerful tools which are meant to facilitate your daily water determination analyses and to contribute to reliable results over the whole lifetime of your instrument. ME-51725145A Markt Support AnaChem . Switzerland Tel. Evaluation of the appropriate titration system (DQ) i. method validation. It outlines specific aspects in developing and maintaining a good routine operation with METTLER TOLEDO Compact Coulometric and Volumetric KF as well as Excellence titrators. +41-44 806 77 11 Fax +41-44 806 73 50 Subject to technical changes.com For more information Mettler-Toledo AG. The GTP KF brochure and the application brochure 38 containing dedicated applications on samples from various industry segments.e. development of SOPs and maintenance of the validated state of the analytical system. evaluation. Installation of the selected analytical system comprising IQ and OQ and training of personnel 3. This brochure specifically focuses on Good Titration Practice in water determination using coulometric and volumetric Karl Fischer Titration. Routine operation including PQ.Good Titration Practice in water determination Good Titration Practice™ (GTP) in general encompasses three important steps: 1. specification of the analytical requirements and purchase decision 2.mt. ©09/2009 Mettler-Toledo AG Printed in Switzerland.

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